WO2010067683A1 - Composition - Google Patents
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- WO2010067683A1 WO2010067683A1 PCT/JP2009/069106 JP2009069106W WO2010067683A1 WO 2010067683 A1 WO2010067683 A1 WO 2010067683A1 JP 2009069106 W JP2009069106 W JP 2009069106W WO 2010067683 A1 WO2010067683 A1 WO 2010067683A1
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- H—ELECTRICITY
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/5329—Insulating materials
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
- H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a composition, and more specifically, as an interlayer insulating film material in a semiconductor element or the like, a coating film having an appropriate uniform thickness can be formed, and an insulating film excellent in dielectric constant characteristics and the like is manufactured.
- the present invention relates to a film-forming composition that can be used.
- a silica (SiO 2 ) film formed by a vacuum process such as a vapor deposition (CVD) method is frequently used as an interlayer insulating film in a semiconductor element or the like.
- a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become.
- an interlayer insulating film having a low dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG has been developed.
- the relative dielectric constant of SiOF film which has been recently studied as a low dielectric constant CVD film, is about 3.3 to 3.5. This film has high hygroscopicity, and the dielectric constant increases while being used. There is a problem of doing.
- the present invention is suitable for use as an interlayer insulating film in a semiconductor element device or the like, can form a film having an appropriate uniform thickness, and has a dielectric constant, Young's modulus, etc. It is an object of the present invention to provide a composition capable of producing an insulating film having excellent characteristics, and an insulating film obtained from the composition.
- the compound (X) is formed by a Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation, or a combination thereof, and the conjugated diene
- the composition according to ⁇ 1> which is a compound having a Diels-Alder reaction addition part for generating a structure and the dienophile structure and having a siloxane structure.
- the compound (X) is formed by a Diels-Alder reaction between a compound (A) having a dienophile structure and having a siloxane structure and a compound (B) having a conjugated diene structure.
- the composition according to ⁇ 2> which is a compound that releases the compound (B) having the conjugated diene structure through reverse Diels-Alder reaction by irradiation, irradiation, or a combination thereof.
- the compound (A) having the siloxane structure is m RSi (O 0.5 ) 3 units (m represents an integer of 8 to 16, and R independently represents a hydrogen atom or a substituent.
- each unit is a compound (I) or a polymer thereof in which each unit shares an oxygen atom in each unit and is linked to another unit to form a cage structure.
- the compound (I) is a compound represented by any one of the following general formulas (Q-1) to (Q-7).
- each R independently represents a hydrogen atom or a substituent.
- W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (X 17 ) (X 18 ) —, or —N (X 19 ) —.
- X 17 to X 19 each independently represents a hydrogen atom or a substituent.
- the amount of the compound (B) having the conjugated diene structure in the compound (X) is 5 to 80% by mass with respect to the total amount of the compound (X).
- ⁇ 3> to ⁇ 6> A composition according to any one of the above.
- a method for producing an insulating film comprising applying the composition according to any one of ⁇ 1> to ⁇ 9> onto a substrate and then hardening the composition.
- ⁇ 12> An electronic device manufactured using the insulating film according to ⁇ 11>.
- each R independently represents a hydrogen atom or a substituent.
- R represents an alkenyl group or an alkynyl group.
- X 1 to X 16 each independently represents a hydrogen atom or a substituent.
- W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2- , -C (X 17 ) (X 18 )-, or -N (X 19 )-.
- X 17 to X 19 each independently represents a hydrogen atom or a substituent.
- an insulating film suitable for use as an interlayer insulating film in a semiconductor element device or the like capable of forming a film having an appropriate uniform thickness, and having excellent characteristics such as dielectric constant and Young's modulus.
- an insulating film obtained from the composition can be provided.
- the composition of the present invention and the insulating film obtained from the composition will be described in detail.
- the compound (X) has a functional group that generates a volatile component by removing a part thereof by heating, light irradiation, radiation irradiation, or a combination thereof, and generates an unsaturated group in the remainder.
- the composition containing compound (X) can be used for various applications as described later.
- a volatile component is removed from a functional group during a high-energy ray irradiation treatment such as heat treatment or light irradiation or radiation irradiation performed during hardening. Desorption proceeds. Due to the generation of volatile components, voids are formed in the film.
- unsaturated groups are formed in the remainder of the functional group, and a curing reaction occurs between the residues. Therefore, it exhibits low dielectric constant, high refractive index, high mechanical strength, high heat resistance, and high oxidative stress resistance, and has a long dielectric constant.
- a stable film can be formed. Note that the optimum conditions for the heating conditions, light irradiation, radiation irradiation conditions, and the like vary depending on the structure of the compound (X) used. Normally, the desorption reaction of volatile components proceeds well under the conditions of heat treatment during film formation described later or irradiation with high energy rays.
- a part of the functional group of the compound (X) is removed by heating, light irradiation, radiation irradiation or a combination thereof to generate a volatile component, and an unsaturated group is generated in the remainder.
- a functional group is not particularly limited, but includes a group containing a dithiocarboxylic acid ester, a group containing a thioester, a group containing an ester, a group containing an azo group, a group containing a carbon-carbon double bond, and a sulfonic acid ester.
- R 30 represents a hydrocarbon group.
- the hydrocarbon group include a saturated hydrocarbon group (for example, an alkyl group) and an aromatic hydrocarbon group (for example, a benzene group). Note that * represents a bonding position.
- X represents S, O, Se, or Te (preferably S or O). Two Xs in (G-1) may be the same or different.
- L represents a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, propylene group, butylene group, isopropylene group), substituted or unsubstituted arylene. Groups (for example, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, etc.) and the like.
- each Y independently represents an alkyl group, an alkenyl group, a silicon atom-containing group, a cycloalkyl group, or an aryl group.
- a plurality of Y may be the same or different.
- L represents a divalent linking group. Specific examples of the linking group are the same as described above.
- a silicon atom containing group is synonymous with the silicon atom containing group represented by R mentioned later.
- the volatile component generated by desorption from the functional group is not particularly limited, and varies depending on the structure of the functional group.
- dithiocarboxylic acid, thioester, thiol, ester nitrogen molecule, amine, alkane, alkene, alkyne, alcohol, sulfonic acid, silane, silanol, carbon dioxide and the like.
- the unsaturated group generated as the remainder is not particularly limited, and may be a group containing a carbon-carbon double bond or a carbon-carbon triple bond.
- an alkenyl group preferably having 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms, more preferably a vinyl group or an allyl group
- an alkynyl group preferably having 1 to 6 carbon atoms, and further having 1 to 6 carbon atoms.
- the ethynyl group is preferred.
- the compound (X) may be a low molecular compound or a high molecular compound (for example, a resin), and the structure thereof is not particularly limited.
- the main skeleton includes polyimide, polyurethane, polyethylene, polyester, polyphenylene ether, polybenzoxazole, polyarylene ether, siloxane structure (Si—O bond), cage structure, diamondoid structure, Examples include diamondoid-arylene structures.
- the compound (X) polyarylene ether, polybenzoxazole, a compound having a siloxane structure (Si—O bond) or a polymer thereof, adamantane, biadamantane, diamantane, triamantane, tetramantane in view of excellent heat resistance And a compound having a cage structure selected from the group consisting of dodecahedrane or a polymer thereof.
- a compound having a siloxane structure (Si—O bond) or a polymer thereof is preferable.
- Compound (X) in which the main skeleton of the compound is polyarylene ether can be synthesized, for example, with reference to JP-T-2003-520864.
- the compound (X) in which the main skeleton of the compound is polybenzoxazole can be synthesized with reference to International Publication No. 2005-019305 pamphlet using a benzoxazole precursor.
- the compound having a siloxane structure is a compound having a siloxane structure composed of silicon atoms and oxygen atoms, and exhibits excellent heat resistance.
- a silsesquioxane compound is preferred from the viewpoint of excellent low dielectric properties and mechanical properties.
- the silsesquioxane compound is a compound having at least a silsesquioxane structure.
- the silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1.5 with respect to the number of silicon atoms) ( Si (O 0.5 ) 3 ).
- the silsesquioxane compound examples include a ladder type, a cage type, an incomplete cage type lacking a part of the cage type, and a mixture thereof. From the viewpoint of heat resistance, the cage type (cage type) Silsesquioxane) is preferred.
- the cage structure is a structure in which the volume is determined by a plurality of rings formed by covalently bonded atoms, and a point located within the volume cannot be separated from the volume without passing through the ring.
- Examples of the compound having the above-described functional group and having a siloxane structure include compounds having the following structure.
- the following compounds can be produced by a known synthesis method.
- cage structure of a compound having a cage structure is the same as described above.
- Specific examples of the cage structure include adamantane, biadamantane, diamantane, triamantane, tetramantane, and dodecahedran. From the viewpoint of low dielectric properties and heat resistance, more preferred is adamantane, biadamantane or diamantane.
- the compound having the cage structure is preferably a polymer of a compound having a cage structure having a polymerizable carbon-carbon double bond and / or carbon-carbon triple bond. Furthermore, a compound represented by any one of the general formulas (H-1) to (H-6) and a polymer thereof are more preferable.
- V 1 to V 8 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, silyl group, acyl group, alkoxy group. Represents a carbonyl group or a carbamoyl group.
- Z 1 to Z 8 each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group.
- m 1 and m 5 each independently represents an integer of 1 to 16 (preferably 1 to 3, more preferably 2).
- n 1 and n 5 each independently represents an integer of 0 to 15 (preferably 0 or 1).
- n 2 , m 3 , m 6 and m 7 each independently represents an integer of 1 to 15 (preferably 1 to 3, more preferably 2).
- n 2 , n 3 , n 6 , and n 7 each independently represents an integer of 0 to 14 (preferably 0 or 1).
- m 4 and m 8 each independently represents an integer of 1 to 20 (preferably 1 to 3, more preferably 2).
- n 4 and n 8 each independently represents an integer of 0 to 19 (preferably 0 or 1).
- the functional group that generates an unsaturated group in the remainder is bonded to any part of the compound represented by the general formula (H-1) to the general formula (H-6) or a polymer thereof. You may do it.
- the polymerization of the compound represented by any of the general formula (H-1) to the general formula (H-6) can be performed by a known polymerization method (for example, radical polymerization).
- ⁇ Compound (Y)> As one of the preferred embodiments of the above compound (X), it is formed by Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof. Examples thereof include a compound (Y) having a Diels-Alder reaction addition part for producing a conjugated diene structure and a dienophile structure and having a siloxane structure. First, the compound (Y) will be described in detail.
- Compound (Y) is a compound having a Diels-Alder reaction addition part and having a siloxane structure.
- the Diels-Alder reaction addition part is a site having a ring structure formed by a Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and is reversed by heating, light irradiation, radiation irradiation or a combination thereof.
- the Diels-Alder reaction proceeds to produce a conjugated diene structure and a dienophile structure.
- the composition containing the compound (Y) can be used for various applications as described later.
- a reverse Diels-Alder reaction occurs during high energy ray irradiation treatment such as heat treatment or light irradiation or radiation irradiation performed at the time of hardening. proceed.
- the Diels-Alder reaction addition part dissociates into a conjugated diene structure and a dienophile structure, and one or both volatilizes to increase the film gap.
- a curing reaction occurs between the residues, a film having a low dielectric constant, a high refractive index, a high mechanical strength, a high heat resistance, a high oxidative stress resistance and a long-term dielectric constant can be formed.
- the conjugated diene structure forming the Diels-Alder reaction addition part is not particularly limited, and a chain conjugated diene structure and a cyclic conjugated diene structure can be used.
- Preferable examples of the conjugated diene structure include the following structures.
- a cyclic conjugated diene structure is preferable because of its excellent stability against heat and the like, and in particular, the (D-1) skeleton, the (D-2) skeleton, the (D-8) skeleton, the (D-9) skeleton, D-10) skeleton, (D-11) skeleton and the like are preferable.
- Y 1 to Y 10 each independently represents a hydrogen atom or a substituent. The definition of the substituent is the same as the substituent in formulas (F-1) to (F-4) described later.
- the dienophile structure forming the Diels-Alder reaction adduct is not particularly limited as long as it is an unsaturated structure that additionally reacts with the above conjugated diene structure to give a cyclic structure, and the alkenyl having a carbon-carbon double bond And alkynyl groups having a carbon-carbon triple bond.
- Preferable examples of the dienophile structure include the following structures. Of these, (E-1) skeleton, (E-2) skeleton, (E-3) skeleton and the like are preferable.
- Y 1 to Y 7 each independently represents a hydrogen atom or a substituent.
- the definition of the substituent is the same as the substituent in formulas (F-1) to (F-4) described later.
- the Diels-Alder reaction addition portion in the present invention is an addition portion obtained by the addition reaction of the conjugated diene structure and the dienophile structure, and the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof.
- the optimum conditions such as heating conditions, light irradiation, and radiation irradiation conditions vary depending on the compounds used.
- the reverse Diels-Alder reaction proceeds under the conditions of heat treatment or high energy ray irradiation during film formation described below.
- the number of Diels-Alder reaction addition parts in the compound (Y) is not particularly limited, and an optimal number is appropriately selected depending on the application.
- the Diels-Alder reaction addition part include structures represented by the following general formula (F-1) to general formula (F-4). With these structures, the progress of the reverse Diels-Alder reaction can be more easily controlled and can be suitably used for applications such as an insulating film described later.
- Y 1 to Y 11 each represents a hydrogen atom or a substituent.
- W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (Y 12 ) (Y 13 ) —, or —N (Y 14 ) —.
- Y 12 to Y 14 each independently represents a hydrogen atom or a substituent.
- * represents a bonding position with the compound (Y).
- Y 1 to Y 11 each represents a hydrogen atom or a substituent.
- substituents include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, or a group obtained by combining them.
- an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a silicon atom-containing group are preferable.
- said each group is synonymous with each group represented by R mentioned later.
- W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (Y 12 ) (Y 13 ) —, or —N (Y 14 ) —.
- —O—, —C (O) —, and —C (Y 12 ) (Y 13 ) — are preferable.
- Y 12 to Y 14 each independently represents a hydrogen atom or a substituent.
- the definition of the substituent represented by Y 12 to Y 14 is the same as the definition of the substituent represented by Y 1 to Y 11 .
- an alkyl group and a cycloalkyl group are preferable.
- the compound (Y) is a compound having a siloxane structure (Si—O bond), and includes a low molecular compound and a high molecular compound (for example, a resin).
- a compound having any siloxane structure may be used as long as the effects of the present invention are not impaired.
- the compound (Y) having a siloxane structure composed of silicon atoms and oxygen atoms exhibits excellent heat resistance.
- the content of the siloxane structure in the compound (Y) is preferably 30 to 100% by mass and more preferably 60 to 100% by mass with respect to the total amount of the compound (Y).
- a silsesquioxane compound is preferred from the viewpoint of excellent low dielectric properties and mechanical properties.
- the silsesquioxane compound is a compound having at least a silsesquioxane structure.
- the silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1.5 with respect to the number of silicon atoms) ( Si (O 0.5 ) 3 ).
- Examples of the silsesquioxane compound include a ladder type, a cage type, an incomplete cage type lacking a part of the cage type, and a mixture thereof.
- the cage type is a structure in which a volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located in the volume cannot be separated from the volume without passing through the ring.
- cage-type silsesquioxane or a polymer thereof can be mentioned from the viewpoint of excellent heat resistance. More preferably, m pieces of RSi (O 0.5) 3 units, other RSi (O 0.5) 3 units and cage silsesquioxane is formed by concatenating each other while sharing the oxygen atoms, and it And the like. Note that m represents an integer of 8 to 16.
- Each R independently represents a hydrogen atom or a substituent, and preferably at least one represents a Diels-Alder reaction addition part.
- M represents an integer of 8-16. From the viewpoint of the effect of lowering the dielectric constant, m is preferably 8, 10, 12, 14, or 16, more preferably 8, 10, 12 from the viewpoint of availability, and most preferably 8, 12 from the viewpoint of polymerization controllability. .
- Examples of the substituent for R preferably have 1 to 20 carbon atoms, and specifically include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, silicon atom-containing groups. Or a combination thereof.
- the alkyl group represented by R may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. You may do it.
- the cycloalkyl group represented by R may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and may have an oxygen atom in the ring. Good. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
- the aryl group represented by R may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
- the aralkyl group represented by R may have a substituent and is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. .
- the alkoxy group represented by R may have a substituent, and is preferably an alkoxy group having 1 to 20 carbon atoms.
- R may have a substituent, and is preferably an alkoxy group having 1 to 20 carbon atoms.
- methoxy group, ethoxy group, propoxy group, n-butoxy group, pentyl An oxy group, a hexyloxy group, a heptyloxy group, etc. are mentioned.
- the silicon atom-containing group represented by R is not particularly limited as long as silicon is contained, but a group represented by the general formula (2) is preferable. * -L 1 -Si- (R 20 ) 3 (2)
- L 1 represents an alkylene group, —O—, —S—, —Si (R 21 ) (R 22 ) —, —N (R 23 ) —, or a divalent linking group obtained by combining these.
- L 1 is preferably an alkylene group, —O—, or a divalent linking group in combination of these.
- the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
- R 21 , R 22 , R 23 and R 20 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or an alkoxy group.
- the definitions of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group and alkoxy group represented by R 21 , R 22 , R 23 and R 20 are the same as those defined above for R, preferably methyl Group, ethyl group, butyl group, cyclohexyl group, vinyl group, ethynyl group and the like.
- the silicon atom-containing group as R is most preferably a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy).
- Examples of the alkenyl group represented by R include a group having a double bond at an arbitrary position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group or silicon atom-containing group.
- the number of carbon atoms is preferably 1 to 12, and more preferably 1 to 6 carbon atoms.
- a vinyl group, an allyl group, etc. are mentioned, and a vinyl group is preferable from the viewpoint of ease of polymerization control and mechanical strength.
- Examples of the alkynyl group represented by R include a group having a triple bond at an arbitrary position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, and silicon atom-containing group.
- the number of carbon atoms is preferably 1 to 12, and more preferably 1 to 6 carbon atoms. From the viewpoints of ease of polymerization control and mechanical strength, an ethynyl group is preferred.
- a preferred embodiment of the compound (Y) is a silsesquioxane compound having the Diels-Alder reaction addition part. More preferably, cage-type silsesquioxane or a polymer thereof having the above-mentioned Diels-Alder reaction addition portion is used. More preferably, a cage-type silsesquioxane or a polymer thereof having at least one Diels-Alder reaction addition part represented by the general formula (F-1) to the general formula (F-4) is used.
- the above-mentioned silane coupling agent having a Diels-Alder reaction addition part, or a hydrolysis condensate thereof can be mentioned. More preferably, the silane coupling agent represented by the following formula
- R 40 4-n —Si— (X) n
- R 40 represents a Diels-Alder reaction addition part represented by the general formula (F-1) to the general formula (F-4).
- X represents an alkoxy group or a halogen element (for example, a chlorine atom).
- n represents an integer of 1 to 3.
- the hydrolysis reaction of the silane coupling agent represented by the general formula (K) can be performed by a known method such as heating.
- the molecular weight of the compound (Y) is not particularly limited, and may be a low molecular compound or a high molecular compound (for example, a resin).
- its weight average molecular weight (M w ) is preferably 2.5 ⁇ 10 4 to 75 ⁇ 10 4 , and is 3.5 ⁇ 10 4 to 35 ⁇ 10 4 . More preferably, it is most preferably 4.5 ⁇ 10 4 to 25 ⁇ 10 4 .
- M n number average molecular weight
- M n number average molecular weight
- the Z + 1 average molecular weight (M Z + 1 ) is preferably 1.5 ⁇ 10 4 to 65 ⁇ 10 4 , and is 2.5 ⁇ 10 4 to 50 ⁇ 10 4 . More preferably, it is most preferably 3.5 ⁇ 10 4 to 35 ⁇ 10 4 .
- the compound (Y) of the present invention preferably contains substantially no component having a molecular weight of 3 million or more, and substantially contains 2 million or more components. It is more preferable not to contain, and it is most preferable not to contain 1 million or more components.
- compound (Y) it can quantify from the GPC chart of a solid content, a HPLC chart, a NMR spectrum, a UV spectrum, IR spectrum, etc.
- the components in the copolymer may be determined by the polymerization charge ratio, but after purifying the solids as necessary, by measuring the NMR spectrum, UV spectrum, IR spectrum, elemental composition, etc. Can also be quantified.
- a compound (Y) formed by Diels-Alder reaction between a compound having a dienophile structure and a siloxane structure and a compound having a conjugated diene structure
- the aspect of (1) is more preferable at the point which is easy to synthesize
- the compound (A) having a dienophile structure and having a siloxane structure and the compound (B) having a conjugated diene structure used in the embodiment of (1) will be described in detail.
- the compound (A) is a compound having a dienophile structure and a siloxane structure.
- the dienophile structure is an unsaturated structure that additionally reacts with the conjugated diene structure to give a cyclic structure.
- the structure is not particularly limited, and examples include the structures exemplified above. Of these, an alkenyl group and an alkynyl group are preferable.
- the compound (A) is a compound having a siloxane structure (Si—O bond), and may be a compound having any siloxane structure as long as the effects of the present invention are not impaired.
- the compound (A) includes a low molecular compound and a high molecular compound (for example, a resin).
- a compound having a siloxane structure composed of silicon atoms and oxygen atoms exhibits excellent heat resistance.
- the content of the siloxane structure in the compound (A) is preferably 30 to 100% by mass and more preferably 60 to 100% by mass with respect to the total amount of the compound (A).
- the compound (A) is preferably a silsesquioxane compound from the viewpoint of excellent low dielectric properties and mechanical properties.
- the silsesquioxane compound is a compound having at least a silsesquioxane structure.
- the silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1.5 with respect to the number of silicon atoms). is there.
- Examples of the silsesquioxane compound include a ladder type, a cage type, an incomplete cage type lacking a part of the cage type, and a mixture thereof. From the viewpoint of heat resistance, stability over time, etc. A mold is preferred.
- the cage type is a structure in which the volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located within the volume cannot be separated from the volume without passing through the ring.
- a silsesquioxane compound having a cage structure is also referred to as a cage silsesquioxane compound.
- the cage silsesquioxane compound As the cage silsesquioxane compound, the cage type formed by connecting m RSi (O 0.5 ) 3 units to other RSi (O 0.5 ) 3 units while sharing the oxygen atom.
- examples thereof include a compound having a structure (hereinafter also referred to as compound (I)) and a polymer having the same as a repeating unit.
- Each R independently represents a hydrogen atom or a substituent.
- M in the compound (I) represents an integer of 8 to 16.
- m is preferably 8, 10, 12, 14, or 16, more preferably 8, 10, 12 from the viewpoint of availability, and most preferably 8, 12 from the viewpoint of polymerization controllability.
- the cage structure represented by compound (I) include compounds represented by the following general formula (Q-1) to general formula (Q-7).
- the free bond in the following represents the position where R is bonded.
- the compound represented by the general formula (Q-6) is most preferable.
- R in the compound (I) independently represents a hydrogen atom or a substituent. Several R may be same or different and at least 1 shows an alkenyl group and an alkynyl group.
- the substituent represented by R has the same definition as the substituent described in detail in the above compound (Y), preferably has 1 to 20 carbon atoms, and specifically includes an alkyl group, a cycloalkyl group, and an aryl group. , An aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, or a combination thereof.
- At least one of R represents an alkenyl group or an alkynyl group.
- two or more of R are preferably an alkenyl group or an alkynyl group, more preferably three or more, and particularly preferably all.
- alkenyl groups and alkynyl groups that are dienophiles are generated in the film by reverse Diels-Alder reaction during hardening, and a crosslinking reaction (curing reaction) by these proceeds. This improves the mechanical strength of the film obtained.
- cage silsesquioxane compound represented by Compound (I) include the following, but the present invention is not limited thereto.
- Compound (I) may be purchased from Aldrich, Hybrid Plastics, Polymers, 20, 67-85, 2008, Journal of Inorganic and Organometallic Polymers, 11 (3), 123-154, 2001 , Journal of Organometallic Chemistry, 542, 141-183, 1997, Journal of Macromolecular Science. A. Chemistry, 44 (7), 659-664, 2007, Chem. Rev., 95, 1409-1430, 1995, Journal of Inorganic and Organometallic Polymers, mers11 (3), 155-164, 2001, Dalton Transactions, 36-39, 2008, Macromolecules, 37 (23), 8517-8522, 2004, Chem. Mater., 8, 1250-1259, 1996, etc. It may be synthesized by a known method described in 1.
- R in the compound (I) of the present invention is a group represented by the following general formula (II).
- the group represented by the general formula (II) can be synthesized by reacting a compound represented by the following general formula (III) with a compound represented by the following general formula (IV).
- the compound represented by the general formula (III) can be synthesized, for example, according to the method described in Angew. Chem. Int. Ed. Engl.,. 1997, 36, No.7, 743-745.
- R 1 independently represents a substituent, and specific examples of the substituent represented by R 1 include an alkyl group, an aryl group, a vinyl group, and an ethynyl group.
- m and R 1 are respectively synonymous with m and R in the compound (I).
- M represents a metal atom (for example, Na, K, Cu, Ni, Mn) or an onium cation (for example, tetramethylammonium).
- M when M is a polyvalent metal atom, it means a form in which a plurality of —O—Si (O 0.5 ) 3 is bonded to the polyvalent metal atom M.
- the reaction between the compound represented by the general formula (III) and the compound represented by the general formula (IV) is carried out, for example, in a solvent by combining the compound represented by the general formula (III) and the general formula (III)
- the compound represented by the general formula (IV) is added in an amount of 1 to 100 times the number of Si-OM groups contained in the compound represented by general formula (IV), and the stirring is usually performed at 0 to 180 ° C. for 10 minutes to 20 hours.
- organic solvents such as toluene, hexane, and tetrahydrofuran (THF) are preferable.
- a base such as triethylamine or pyridine may be added.
- R in general formula (Q-8) and general formula (Q-9) each independently represents a hydrogen atom or a substituent.
- R may be same or different and at least 1 shows an alkenyl group and an alkynyl group.
- the definition of the substituent represented by R is synonymous with the definition of R in the said compound (I).
- One preferred embodiment of the compound (A) having a siloxane structure includes a polymer having the compound (I) as a repeating unit, and includes a polymer of a plurality of different compounds (I). Also good. In that case, the copolymer which consists of several different compound (I) may be sufficient, and the mixture of a homopolymer may be sufficient.
- the compound (A) having a siloxane structure may be a copolymer with a compound other than the compound (I).
- the compound used in that case is preferably a compound having a plurality of polymerizable carbon-carbon unsaturated bonds or SiH groups.
- preferred compounds include vinyl silanes, vinyl siloxanes, phenylacetylenes, vinyl adamantanes, [(HSiO 0.5 ) 3 ] 8 and the like.
- the component derived from the compound (I) is preferably 50% by mass or more, and most preferably 70% by mass or more in the copolymer.
- the content of the unreacted compound (I) contained in the production of the polymer having the compound (I) as a repeating unit is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total solid content. And most preferably 7% by mass or less. Thereby, the coated surface state can be improved.
- the total solid content means a total component of the polymer of compound (I) and an unreacted product.
- the weight average molecular weight (M w ) of the compound (A) having a siloxane structure is preferably 2.0 ⁇ 10 4 to 70 ⁇ 10 4 excluding the compound (I) monomer, It is more preferably 10 4 to 30 ⁇ 10 4 , and most preferably 4.0 ⁇ 10 4 to 20 ⁇ 10 4 .
- the number average molecular weight (M n ) of the compound (A) having a siloxane structure is preferably 1.0 ⁇ 10 4 to 30 ⁇ 10 4 excluding the compound (I) monomer, It is more preferably 10 4 to 15 ⁇ 10 4 , and most preferably 2.0 ⁇ 10 4 to 10 ⁇ 10 4 .
- the Z + 1 average molecular weight (M Z + 1 ) of the compound (A) having a siloxane structure is preferably 1.0 ⁇ 10 4 to 60 ⁇ 10 4 except for the compound (I) monomer, and 2.0 ⁇ It is more preferably 10 4 to 45 ⁇ 10 4 , and most preferably 3.0 ⁇ 10 4 to 30 ⁇ 10 4 .
- the polymer preferably does not substantially contain a component having a molecular weight of 3 million or more, more preferably does not substantially contain a component having a molecular weight of 2 million or more. Most preferably, it contains no more than 10,000 components.
- unreacted alkenyl group and alkynyl group derived from compound (I) remain in the polymer of compound (I).
- alkenyl groups and alkynyl groups derived from compound (I) 10 to 90 It is preferable that the mol% remains unreacted, 20 to 80 mol% is preferably left unreacted, and 30 to 70 mol% is most preferably left unreacted. If it is in the said range, the sclerosis
- Their content is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 10% by mass, most preferably from 0.1 to 5% by mass, based on the total amount of the polymer. About these, it can quantify from the NMR spectrum etc. of a composition.
- the polymerization reaction of the carbon-carbon unsaturated bond of compound (I) may be any polymerization reaction.
- radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, transition Examples include metal catalyst polymerization.
- the hydrosilylation reaction is performed, for example, by the compound of the present invention and a compound containing two or more SiH groups in the molecule (for example, bis (dimethylsilyl) ethane, 1,1,3,3-tetramethyldimethyl).
- Dissolve siloxane etc. in an organic solvent eg toluene, xylene etc.
- catalyst eg Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex etc.
- sol-gel reaction include the methods described in the application of sol-gel method to nanotechnology (CMC, 2005) and the development of application of sol-gel method (CMC, 2008).
- a polymerization reaction of a carbon-carbon unsaturated bond of compound (I) is preferable, and radical polymerization is most preferable.
- Synthetic methods include a batch polymerization method in which the compound (I) and the initiator are dissolved in a solvent and heated to perform polymerization, and the compound (I) is dissolved in a solvent and heated, and the initiator solution is maintained for 1 to 10 hours. Examples thereof include a dropping polymerization method (continuous addition) that is added dropwise over a period of time, a split addition polymerization method (split addition) in which an initiator is divided into a plurality of times and added. Split addition and continuous addition are preferred because the film strength and molecular weight reproducibility are further improved.
- the reaction temperature of the polymerization reaction in the present invention is usually 0 ° C. to 200 ° C., preferably 40 ° C. to 170 ° C., more preferably 80 ° C. to 160 ° C.
- it is preferable to make it react under inert gas atmosphere for example, nitrogen, argon, etc.
- the oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
- the concentration of compound (I) in the reaction solution during polymerization is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less with respect to the total mass of the reaction solution. More preferred is 10% by mass or less.
- an ester solvent is a solvent having an ester group in the molecule.
- the solvent include water, alcohol solvents such as methanol, ethanol, propanol and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate.
- Amide solvents such as carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, chlorobenzene, 1,2,4-trichlorobenzene, hexane, heptane, octane, Aliphatic hydrocarbon solvents such as cyclohexane can be used.
- these solvents more preferred are ester solvents, ether solvents and aromatic hydrocarbon solvents, and specifically, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate, propion.
- Methyl acid, propylene glycol monomethyl ether acetate, tetrahydrofuran, diphenyl ether, anisole, toluene, xylene, mesitylene and t-butylbenzene are preferred, and ethyl acetate, butyl acetate, diphenyl ether, anisole, mesitylene and t-butylbenzene are particularly preferred. These may be used alone or in admixture of two or more.
- the boiling point of the solvent is preferably 65 ° C. or higher so that the reaction solution can be heated to a temperature necessary for decomposing the polymerization initiator during the reaction.
- the polymerization reaction of compound (I) is preferably performed in the presence of a nonmetallic polymerization initiator.
- the polymerization can be carried out in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating.
- a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating.
- an organic peroxide or an organic azo compound is particularly preferably used.
- organic peroxides include ketone peroxides such as Perhexa H, peroxyketals such as Perhexa TMH, hydroperoxides such as Perbutyl H-69, Parkmill D, and Perbutyl C, which are commercially available from Nippon Oil & Fats Co., Ltd.
- Dialkyl peroxides such as perbutyl D, diacyl peroxides such as Nyper BW, peroxyesters such as perbutyl Z and perbutyl L, peroxydicarbonates such as perroyl TCP, diisobutyryl peroxide, cumylperoxyneodeca Noate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4 -T-Buchi Chlohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Hexyl peroxypivalate,
- organic azo compounds include azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70 that are commercially available from Wako Pure Chemical Industries, Ltd., VA-080.
- Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidines such as V-50 and VA-057
- azo ester compounds such as V-601, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2- Azobis (2-methylpropionitrile), 2,2-azobis (2,4-dimethylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 1- [ (1-cyano-1-methylethyl) azo] formamide, 2,2-azobis ⁇ 2-methyl-N
- the polymerization initiator is preferably an organic azo compound in view of the safety of the reagent itself and the molecular weight reproducibility of the polymerization reaction. Among them, an azo ester compound such as V-601 that does not incorporate harmful cyano into the polymer is preferable.
- the 10-hour half-life temperature of the polymerization initiator is preferably 100 ° C. or lower. If the 10-hour half-life temperature is 100 ° C. or less, it is easy to prevent the polymerization initiator from remaining at the end of the reaction. Only one polymerization initiator or a mixture of two or more polymerization initiators may be used.
- the amount of the polymerization initiator used is preferably 0.0001 to 2 mol, more preferably 0.003 to 1 mol, and particularly preferably 0.001 to 0.5 mol with respect to 1 mol of the monomer.
- the weight average molecular weight (M w ) of the polymer at the end of the polymerization reaction is preferably 2 ⁇ 10 4 to 50 ⁇ 10 4 , more preferably 3 ⁇ 10 4 to 40 ⁇ 10 4. Most preferably, it is 10 4 to 40 ⁇ 10 4 .
- the Z + 1 average molecular weight (M Z + 1 ) of the polymer at the end of the polymerization reaction is preferably 10 ⁇ 10 4 to 60 ⁇ 10 4 , more preferably 9 ⁇ 10 4 to 55 ⁇ 10 4 , and 8 ⁇ 10 4. Most preferred is ⁇ 40 ⁇ 10 4 .
- the polymer at the end of the polymerization reaction is preferably substantially free of components having a molecular weight of 300 ⁇ 10 4 or more, more preferably substantially free of components of 200 ⁇ 10 4 or more, and 100 ⁇ 10 4 or more. It is most preferable not to contain these components. When these molecular weight conditions are satisfied at the time of polymerization, a film-forming composition having a good coated surface and a small film loss upon firing can be produced with high yield.
- the reaction solution obtained by subjecting the compound (I) to the polymerization reaction may be used as it is, but it is preferable to carry out a purification treatment after completion of the reaction.
- Purification methods include water-washing and a liquid-liquid extraction method that removes residual monomers and oligomer components by combining with an appropriate solvent, ultrafiltration that extracts only those with a specific molecular weight or less, centrifugation, and column A purification method in a solution state such as chromatography, a reprecipitation method in which the polymer solution is solidified in the poor solvent by dropping the polymer solution into the poor solvent, and the residual weight is removed by filtration.
- a usual method such as a purification method in a solid state such as washing the combined slurry with a poor solvent can be applied.
- the polymer is precipitated as a solid by contacting a solvent in which the polymer is hardly soluble or insoluble (poor solvent) in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.
- the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon or halogenated carbonization depending on the type of polymer.
- It can be suitably selected from hydrogen, nitro compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like.
- a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
- the amount of the precipitation or reprecipitation solvent to be used can be appropriately selected in consideration of efficiency, yield and the like. More preferably, it is 300 to 1000 parts by mass.
- the temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.).
- the precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
- the precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
- the polymer may be once precipitated and separated, and then dissolved again in a good solvent, and the polymer may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the polymerization reaction, the polymer is brought into contact with a hardly soluble or insoluble solvent, the polymer is precipitated (step a), the polymer is separated from the solution (step b), and again dissolved in a good solvent to be recycled.
- a combined solution A is prepared (step c), and then a solvent in which the polymer is hardly soluble or insoluble is added to the polymer solution A in a volume amount less than 10 times that of the polymer solution A (preferably a volume of 5 times or less).
- the method may include depositing a polymer solid by contacting (step d) and separating the precipitated polymer (step e).
- a polymer solid by contacting (step d) and separating the precipitated polymer (step e).
- the good solvent ethyl acetate, butyl acetate, toluene, methyl ethyl ketone, tetrahydrofuran and the like are preferable.
- As the good solvent it is preferable to use an equal mass to 50 times mass of the polymer of the present invention, and it is more preferable to use 2 times mass to 20 times mass.
- a polymerization inhibitor may be added in order to suppress unnecessary polymerization.
- the polymerization inhibitor include 4-methoxyphenol, 2,6-bis (1,1-dimethylethyl) -4-methylphenol, catechol and the like.
- the compound (B) having a conjugated diene structure is a compound having a conjugated diene structure capable of Diels-Alder reaction with the compound (A). It does not specifically limit as a conjugated diene structure, The example structure mentioned above etc. are mentioned. In addition, the compound (B) which has a conjugated diene structure may be used individually by 1 type, and may use 2 or more types together.
- any compound having a conjugated diene structure can be used as the compound having a conjugated diene structure, and a low molecular weight diene capable of volatilization is preferred.
- Examples of the compound having a conjugated diene structure are described as diene in Dienes in the Diels-Alder Reaction (Wiley-Interscience, 1990), The Diels-Alder Reaction: Selected Practical Methods (John Wiley & Sons Inc, 2002). And the like.
- the compound having a conjugated diene structure include hydrocarbon compounds having a conjugated diene structure, and more specifically, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, cyclopentadiene, pentamethylcyclopentadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3,7-octatriene, cyclooctadiene, norbornadiene, 1,3 , 5,5-tetramethyl-1,3-cyclohexadiene, ⁇ -ferrand
- dicyclopentadiene dicyclopentadiene, cyclopentadiene, pentamethylcyclopentadiene, ⁇ -ferrandylene, ⁇ -terpinene, and tetraphenylcyclopentadienone are preferable.
- compounds represented by general formula (B-1) to general formula (B-3) can be given.
- the Diels-Alder reaction proceeds with good yield, the dielectric constant of the resulting film is further reduced, and a higher Young's modulus and good stability over time are obtained.
- X 1 to X 16 each independently represents a hydrogen atom or a substituent.
- W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (X 17 ) (X 18 ) —, or —N (X 19 ) —.
- X 17 to X 19 each independently represents a hydrogen atom or a substituent.
- X 1 to X 16 each independently represents a hydrogen atom or a substituent.
- the substituents represented by X 1 to X 16 have the same meanings as the substituents represented by Y 1 to Y 11 in formulas (F-1) to (F-4). Of these, an alkyl group, a cycloalkyl group, an aryl group, a silicon atom-containing group and the like are preferable.
- X 17 to X 19 each independently represent a hydrogen atom or a substituent.
- the substituents represented by X 17 to X 19 have the same meanings as the substituents represented by X 1 to X 16 above.
- a coating film containing the compound (Y) obtained by bonding the compound (B) having such a diene structure to the compound (A) having a siloxane structure heating, light irradiation, radiation irradiation, or a combination thereof is performed.
- the reverse Diels-Alder reaction can be advanced by carrying out the hardening process used.
- the compound (B) having a diene structure that acts as a pore-forming agent volatilizes from the compound (Y) to increase the film gap and further causes a curing reaction between the residues, resulting in a low dielectric constant and a high refractive index.
- the addition amount (content) of the compound having a diene structure is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass with respect to the total amount of the compound (Y). If it is the said range, the production
- Addition amount of compound having diene structure is NMR spectrum, thermogravimetric analysis (TGA) to measure mass change while heating or cooling, differential thermal analysis (DTA) to measure change of specific heat and reaction heat, differential scanning calorimetry Can be quantified by (DSC).
- the compound (Y) synthesized using the compound (B) when used, the compound (B) that acts as a pore-forming agent at the time of hardening is released, and at the same time, a dienophile structure that can be a cross-linked portion is generated.
- pore formation and membrane crosslinking can proceed simultaneously in the same region in the film, and a large number of pores having smaller sizes and uniform sizes can be formed uniformly in the film.
- the pore-forming agents usually aggregate to form a large domain, and the region where the pore-forming agent volatilizes and the region where the cross-linked structure is formed are separated.
- the conditions under which the Diels-Alder reaction is performed between the compound (A) and the compound (B) are appropriately selected depending on the type of compound used.
- the reaction solvent for performing the Diels-Alder reaction is not particularly limited as long as the compound to be used dissolves and does not affect the reaction.
- the reaction temperature is not particularly limited, but is usually 25 ° C to 250 ° C, preferably 50 ° C to 200 ° C, more preferably 80 ° C to 200 ° C.
- the concentration of the compound (A) in the reaction solution is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total amount of the reaction solution.
- concentration range By setting the concentration range, the generation of impurities such as gelling components can be suppressed.
- oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
- a polymerization inhibitor in order to suppress the polymerization reaction.
- the polymerization inhibitor include 4-methoxyphenol, 2,6-bis (1,1-dimethylethyl) -4-methylphenol, catechol and the like. Of these, 4-methoxyphenol and 2,6-bis (1,1-dimethylethyl) -4-methylphenol are particularly preferable.
- the addition amount of the polymerization inhibitor is preferably 5% by mass or more based on the total amount of the compound (A) having a siloxane structure.
- the composition of the present invention contains the above compound (X).
- the composition of the present invention may be a solution in which the compound (X) is dissolved in a solvent (for example, an organic solvent), or may be a solid containing a reaction product of the compound (X).
- the composition of the present invention can be used in various applications, and the type of the content of the compound (X) and the additive to be added is determined according to the purpose. Applications include, for example, for producing a film (for example, an insulating film) (film forming composition), a low refractive index film, a low refractive index material, a gas adsorbing material, a resist material, and the like.
- content of compound (X) is not specifically limited among solid content contained in a composition, When using for the film formation mentioned later, it is 70 mass% or more with respect to the total solid content. More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. As these contents in the solid content increase, the coating property is improved and a film having a lower dielectric constant can be formed.
- solid content means the solid component which comprises the film
- the composition of the present invention may contain a solvent. That is, it is preferable to use the compound (X) by dissolving it in an appropriate solvent and coating it on a support.
- a solvent the solvent which melt
- preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl.
- Ether propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, Mention may be made of mesitylene and diisopropylbenzene.
- a solution obtained by dissolving the composition of the present invention in an appropriate solvent is also included in the scope of the composition of the present invention.
- the total solid concentration in the composition is preferably 1 to 30% by mass with respect to the total amount of the composition, and is appropriately adjusted according to the purpose of use.
- the total solid content concentration of the composition is 1 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability of the coating solution is further improved.
- the composition of the present invention may contain a polymerization initiator.
- the polymerization initiator when it is necessary to harden the composition of the present invention at a low temperature, the polymerization initiator is preferably included.
- the type of the polymerization initiator is not particularly limited, and examples thereof include a polymerization initiator used in the polymerization of the compound (I) described above. For this purpose, it is also possible to use initiators that cause polymerization by radiation.
- the metal content as an impurity is preferably sufficiently small.
- the metal concentration in the composition can be measured with high sensitivity by the ICP-MS method or the like, and the metal content other than the transition metal in that case is preferably 30 ppm or less, more preferably 3 ppm or less, and particularly preferably 300 ppb or less.
- the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the pre-baking and thermosetting processes described later, the content is lower. It is preferably 10 ppm or less, more preferably 1 ppm or less, particularly preferably 100 ppb or less.
- the metal concentration in the composition can also be evaluated by performing total reflection X-ray fluorescence measurement on the film obtained using the composition.
- W line is used as the X-ray source
- K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, and each is 100 ⁇ 10 10 cm ⁇ 2 or less. Is more preferably 50 ⁇ 10 10 cm ⁇ 2 or less, and particularly preferably 10 ⁇ 10 10 cm ⁇ 2 or less. Further, Br which is halogen can be observed, and the residual amount is preferably 10000 ⁇ 10 10 cm ⁇ 2 or less, more preferably 1000 ⁇ 10 10 cm ⁇ 2 or less, particularly preferably 400 ⁇ 10 10 cm ⁇ 2 or less. is there.
- Cl can be observed as halogen
- the remaining amount is preferably 100 ⁇ 10 10 cm ⁇ 2 or less, more preferably 50 ⁇ 10 10 cm ⁇ 2 or less from the viewpoint of damaging a CVD apparatus, an etching apparatus, or the like. Particularly preferably, it is 10 ⁇ 10 10 cm ⁇ 2 or less.
- the composition of the present invention includes a radical generator and colloidal silica as long as the properties (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) of the film obtained using the composition are not impaired.
- Additives such as surfactants and adhesives may be added.
- any colloidal silica may be used in the composition of the present invention as long as the object of the present invention is not impaired.
- a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water usually having an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of about 5 to 40% by mass It is.
- any surfactant may be used in the composition of the present invention as long as the object of the present invention is not impaired.
- nonionic surfactants anionic surfactants, cationic surfactants, and the like
- silicone surfactants fluorine-containing surfactants, polyalkylene oxide surfactants, acrylic surfactants Agents. Only one type of surfactant may be used, or two or more types may be used in combination.
- silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable.
- the addition amount of the surfactant used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the composition. More preferably.
- the silicone-based surfactant is a surfactant containing at least one Si atom.
- the silicone surfactant used in the present invention may be any silicone surfactant, and preferably has a structure containing alkylene oxide and dimethylsiloxane. A structure including the following chemical formula is more preferable.
- R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- x is an integer of 1 to 20
- m and n are each independently an integer of 2 to 100.
- a plurality of R may be the same or different.
- silicone-based surfactant used in the present invention examples include BYK306, BYK307 (manufactured by Big Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 (manufactured by Troy Chemical). Can be mentioned.
- the nonionic surfactant used in the present invention may be any nonionic surfactant as long as the object of the present invention is not impaired.
- polyoxyethylene alkyl ethers polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, sorbitan fatty acid esters, fatty acid-modified polyoxyethylenes, polyoxyethylene-polyoxypropylene block copolymers, etc. Can do.
- Fluorine-containing surfactant used in the present invention may be any fluorine-containing surfactant as long as the object of the present invention is not impaired.
- fluorine-containing surfactant for example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.
- the acrylic surfactant used in the present invention may be any acrylic surfactant as long as the object of the present invention is not impaired.
- a (meth) acrylic acid type copolymer etc. are mentioned.
- any adhesion promoter may be used in the composition of the present invention as long as the object of the present invention is not impaired.
- adhesion promoters are preferred as adhesion promoters. Only one type of adhesion promoter used in the present invention may be used, or two or more types may be used in combination.
- the preferred use amount of the adhesion promoter is not particularly limited, but it is usually preferably 10% by mass or less, particularly preferably 0.05 to 5% by mass with respect to the total solid content in the composition.
- the composition of the present invention is preferably used for film formation after removing insolubles, gelled components and the like by filter filtration.
- the pore size of the filter used at that time is preferably 0.005 to 0.5 ⁇ m, more preferably 0.005 to 0.2 ⁇ m, and most preferably 0.005 to 0.1 ⁇ m.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene, polypropylene, or nylon, and more preferably polytetrafluoroethylene, polyethylene, or nylon.
- the composition of the present invention can be used for various applications as described above.
- it can be used for producing an insulating film (hereinafter referred to as a film-forming composition as appropriate).
- the insulating film obtained by using the film forming composition of the present invention can be obtained by any method such as spin coating method, roller coating method, dip coating method, scanning method, spray method, bar coating method, etc.
- a substrate such as a silicon wafer, a SiO 2 wafer, a SiN wafer, glass, or a plastic film
- the solvent can be removed by heat treatment as necessary.
- a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method.
- the clean track series manufactured by Tokyo Electron
- D-spin series manufactured by Dainippon Screen
- SS series manufactured by Tokyo Ohka Kogyo Co., Ltd.
- the spin coating conditions may be any rotational speed, but a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate from the viewpoint of in-plane uniformity of the insulating film.
- the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable.
- the spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput.
- processing edge rinse, back rinse
- the method of heat treatment is not particularly limited, but it is possible to apply commonly used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. Can do.
- a heating method using hot plate heating or furnace is preferable.
- a commercially available apparatus can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron), D-Spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo) can be preferably used.
- the furnace As the furnace, ⁇ series (manufactured by Tokyo Electron) and the like can be preferably used.
- the composition of the present invention is preferably hardened after being coated on a substrate to form a coating film.
- the hardened film means that the composition (coating film) on the substrate is cured and solvent resistance is given to the film.
- heat treatment for example, a polymerization reaction at the time of post-heating of the vinyl group remaining in the compound (X) can be used.
- the conditions for this post-heating treatment are preferably 100 to 600 ° C., more preferably 200 to 500 ° C., particularly preferably 200 ° C. to 450 ° C., preferably 1 minute to 3 hours, more preferably 1 minute to 2 hours, Particularly preferred is the range of 1 minute to 1 hour.
- the post-heating treatment may be performed in several times. Further, this post-heating is particularly preferably performed in a nitrogen atmosphere in order to prevent thermal oxidation by oxygen.
- the film may be hardened by causing a polymerization reaction of a vinyl group or an ethynyl group remaining in the compound (X) by irradiating with high energy rays such as light irradiation and radiation irradiation instead of heat treatment.
- high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
- the energy when an electron beam is used as the high energy beam is preferably 0.1 to 50 keV, more preferably 0.2 to 30 keV, and particularly preferably 0.5 to 20 keV.
- the total dose of the electron beam is preferably 0.01 to 5 ⁇ C / cm 2 , more preferably 0.01 to 2 ⁇ C / cm 2 , and particularly preferably 0.01 to 1 ⁇ C / cm 2 .
- the substrate temperature at the time of irradiation with an electron beam is preferably 0 to 500 ° C., more preferably 20 to 450 ° C., and particularly preferably 20 to 400 ° C.
- the pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa.
- the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen.
- a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam.
- the electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.
- Ultraviolet rays may be used as the high energy rays.
- the irradiation wavelength region when using ultraviolet rays is preferably 160 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁇ 2 immediately above the substrate.
- the substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C.
- the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa.
- the film may be hardened by performing heat treatment and high energy ray treatment irradiation such as light irradiation and radiation irradiation simultaneously or sequentially.
- the film thickness when forming the insulating film is a dry film thickness of about 0.05 to 1.5 ⁇ m with a single coating, and a coating with a thickness of about 0.1 to 3 ⁇ m with a second coating. Can do. Since the cage structure does not decompose during firing, it is preferable that groups (hydroxyl groups, silanol groups, etc.) that nucleophilically attack Si atoms are not substantially present during the production of the composition and film.
- the film-forming composition of the present invention is applied onto a substrate (usually a substrate having metal wiring) by, for example, spin coating, preliminarily heat-treated to dry the solvent, and then 300
- An insulating film having a low dielectric constant can be formed by performing a final heat treatment (annealing) at a temperature of 430 ° C. to 430 ° C.
- the thickness of the insulating film obtained from the film forming composition described above is not particularly limited, but is preferably 0.005 to 10 ⁇ m, more preferably 0.01 to 5.0 ⁇ m, More preferably, it is -1.0 ⁇ m.
- the thickness of the insulating film of the present invention means a simple average value when three or more arbitrary positions are measured with an optical interference type film thickness measuring instrument.
- the dielectric constant of the insulating film obtained by the above-described method of the present invention varies depending on the material used, but at a measurement temperature of 25 ° C., the dielectric constant is preferably 2.4 or less, that is, 1.8 to 2.4. Preferably there is.
- the Young's modulus of the insulating film of the present invention varies depending on the material used, but is preferably 2.0 to 15.0 GPa, more preferably 3.0 to 15.0 GPa.
- the film obtained from the film-forming composition described above is preferably a porous film, and the pore diameter (hereinafter also referred to as the maximum distribution diameter) indicating the maximum peak in the pore distribution curve of the pores in the porous film is It is preferable that it is 5 nm or less. When the maximum distribution diameter is 5 nm or less, it is possible to achieve both excellent mechanical strength and relative dielectric constant characteristics.
- the maximum distribution diameter is more preferably 3 nm or less.
- the lower limit of the maximum distribution diameter is not particularly limited, but a lower limit that can be measured by a known measuring apparatus is 0.5 nm.
- the maximum distribution diameter means a hole diameter showing a maximum peak in a hole distribution curve obtained by a nitrogen gas adsorption method.
- a barrier layer for preventing metal migration may be provided on the wiring side surface in the wiring structure.
- the layer may be divided into a plurality of layers with other kinds of materials as required.
- the insulating film of the present invention may be used by forming a laminated structure with other Si-containing insulating films or organic films. It is preferable to use it laminated with a hydrocarbon film.
- the insulating film obtained using the film forming composition of the present invention can be etched for copper wiring or other purposes. Etching may be either wet etching or dry etching, but dry etching is preferred. For dry etching, either ammonia-based plasma or fluorocarbon-based plasma can be used as appropriate. For these plasmas, not only Ar but also gases such as oxygen, nitrogen, hydrogen, and helium can be used. In addition, after the etching process, ashing can be performed for the purpose of removing the photoresist or the like used for the processing, and further, cleaning can be performed to remove a residue at the time of ashing.
- the insulating film obtained using the film-forming composition of the present invention can be subjected to CMP after the copper wiring processing to flatten the copper plating portion.
- CMP slurry chemical solution
- a commercially available slurry for example, manufactured by Fujimi, manufactured by Rodel Nitta, manufactured by JSR, manufactured by Hitachi Chemical, etc.
- a CMP apparatus a commercially available apparatus (Applied Materials Co., Ltd., Ebara Corporation, etc.) can be used suitably. Further, cleaning can be performed to remove slurry residues after CMP.
- the insulating film of the present invention can be used for various purposes, and can be particularly suitably used for electronic devices.
- An electronic device means a wide range of electronic equipment including a semiconductor device and a magnetic recording head.
- it is suitable as an insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, semiconductor interlayer insulating film, etching stopper film, surface
- protective films and buffer coat films it is used as LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper clad cover coats, solder resist films, liquid crystal alignment films, etc. be able to. It can also be used as a surface protective film, an antireflection film, or a retardation film for optical devices.
- each compound corresponds to the compound described as an exemplary compound of said compound (I).
- the unreacted compound (Im) was 0.2% by mass or less, and no component having a molecular weight of 3 million or more was observed.
- 1 H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, a proton peak derived from an alkyl group formed by polymerization of a vinyl group (0.2 to 3.0 ppm) and a proton peak of a remaining vinyl group ( 4.9-6.8 ppm) was observed at an integration ratio of 2.2 / 5.8.
- Resin A-6 to Resin A-11 were synthesized with reference to the above production example.
- Table 1 shows the type and composition of the compound (I) used in the synthesis of each resin, and the weight average molecular weight and number average molecular weight.
- thermogravimetric analysis TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rising at 20 ° C / min), a 28% weight loss was observed at 340 ° C, and cyclopentadiene in resin X-1 The addition amount (mass%) of was confirmed.
- thermogravimetric analysis TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rising at 20 ° C / min), 44% weight loss was observed at 336 ° C, and pentamethyl in resin X-2 The addition amount (mass%) of cyclopentadiene was confirmed.
- thermogravimetric analysis TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rise at 20 ° C / min), 14% weight loss was observed at 330 ° C, and pentamethyl in resin X-3 The addition amount (mass%) of cyclopentadiene was confirmed.
- Resins X-4 to X-12 were synthesized.
- Table 1 shows the types of the resin A and the diene compound used for the synthesis of each resin, the weight average molecular weight, and the number average molecular weight.
- the addition amount of the diene B in Table 1 is the mass% (wt%) of the diene B in the resin X.
- Resins X-23 to X-28 were synthesized using Resins H-1 to H-5.
- Table 3 shows the types of resin H and diene compound used in the synthesis of each resin, and the weight average molecular weight and number average molecular weight.
- the amount of diene B added in Table 3 is the mass% (wt%) of diene B in the resin X.
- composition ⁇ Preparation of composition>
- the resin obtained above was dissolved in a solvent as shown in Table 4 below, and a solution having a solid content of 8% by mass was prepared for each.
- the obtained solution was filtered through a 0.1 ⁇ m tetrafluoroethylene filter, and then applied onto a 4 inch silicon wafer by spin coating, and then on a hot plate at 110 ° C. for 1 minute, then at 200 ° C. for 1 minute.
- the substrate was preliminarily dried to form a coating film having a thickness of 400 nm.
- the obtained coating film was cured by any of the following methods.
- Heating It was heated in a clean oven at 400 ° C. for 60 minutes under a nitrogen atmosphere by a clean oven CLH-21CD (III) manufactured by Koyo Thermo.
- CLH-21CD (III) manufactured by Koyo Thermo (2) EB irradiation An electron acceleration voltage of 20 keV and an electron beam dose of 1 ⁇ Ccm ⁇ 2 were irradiated for 5 minutes under the conditions of Ar atmosphere, pressure of 100 kPa, and substrate temperature of 350 ° C. using Mini-EB manufactured by USHIO.
- the obtained cured film was evaluated by the following method. The results are shown in Table 4.
- the content of the surfactant represents mass% with respect to the total amount of the composition (coating liquid).
- the content of the adhesion promoter is represented by mass% with respect to the total solids in the composition (coating liquid).
- ⁇ Relative permittivity> Using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, the capacity value at 1 MHz (measurement temperature: 25 ° C.) was used for calculation. ⁇ Young's modulus> The Young's modulus was measured using MTS nanoindenter SA2. ⁇ Stability of relative permittivity over time> The obtained wafer was left in an atmosphere of 23 ° C. and 40% RH (relative humidity), and the relative dielectric constant was measured by the above method after 4 weeks. Those in which the relative dielectric constant change amount was in the range of ⁇ 0.1 were indicated as ⁇ , and those not in the range were indicated as ⁇ .
- the relative permittivity is low by various curing methods such as heating, EB irradiation, UV irradiation, and the relative permittivity is stable over time and heat resistance. It was confirmed that an excellent film having a high Young's modulus can be obtained. On the other hand, the films obtained in Comparative Examples 1 and 2 that did not release the diene compound during the curing treatment had a high relative dielectric constant and a low Young's modulus. It was also inferior in terms of the relative dielectric constant stability over time and heat resistance.
- the obtained composition was applied on a 4-inch silicon wafer by spin coating, and then the substrate was dried on a hot plate at 80 ° C. for 5 minutes and at 200 ° C. for 5 minutes, and further in an oven in a nitrogen atmosphere at 400 ° C. Was baked for 60 minutes to form a film having a thickness of 400 nm.
- the relative dielectric constant was 2.1
- the Young's modulus was 5.4 MPa
- the temporal stability of the dielectric constant was ⁇ .
- the obtained cured film is cut into a 2.0 cm ⁇ 0.5 cm rectangle together with the wafer and placed in a gas adsorption measurement cell, and a gas with nitrogen gas is used with a pore distribution / specific surface area measurement device AUTOSORB-1 manufactured by QUANTACHROME.
- Adsorption measurement was performed.
- the data after measurement is analyzed by the N2 / DFT (N2 at 77K on silica (Cylinder pore, NLDFT equilibrium model)) method, and the maximum frequency diameter (maximum peak) of the obtained pore distribution (hole distribution) is the maximum distribution.
- the diameter The maximum frequency diameters of Examples 1, 2, and 17 were 2.5 nm, 2.8 nm, and 1.9 nm, respectively, and Comparative Examples 1 and 2 were 7.8 nm and 9.2 nm, respectively.
Abstract
Description
一方、有機ポリマーに低分子のカゴ型化合物を添加した溶液を塗布することによって、低屈折率、低密度の膜を得る試みも知られている(特許文献1参照)。しかし、カゴ型化合物単量体を添加する方法では、得られる膜の誘電率およびヤング率などの諸特性が実用的な観点からは必ずしも満足いくものではなく、さらに塗布面状悪化や焼成時の膜減りが大きいなどの問題点があった。 Under such circumstances, a method of reducing the dielectric constant by forming pores by adding a high-boiling solvent or a thermally decomposable compound to organopolysiloxane as an insulating film material excellent in insulation, heat resistance, and durability has been proposed. ing. However, in such a porous film, even if the dielectric constant characteristics are lowered due to the porous film, mechanical strength is lowered and the dielectric constant is increased due to moisture absorption. Further, since holes connected to each other are formed, there has been a problem that copper used for wiring diffuses into the insulating film.
On the other hand, an attempt to obtain a film having a low refractive index and a low density by applying a solution obtained by adding a low molecular weight cage compound to an organic polymer is also known (see Patent Document 1). However, in the method of adding the cage compound monomer, the properties such as the dielectric constant and Young's modulus of the obtained film are not always satisfactory from a practical viewpoint, and further, the coated surface condition deteriorates and the firing There were problems such as large film loss.
<1> 加熱、光照射、放射線照射またはそれらの組み合わせにより、その一部が脱離して揮発性成分を生じ、残部に不飽和基を生成する官能基を有する化合物(X)を含有する組成物。
<2> 前記化合物(X)が、共役ジエン構造とジエノフィル構造とのディールス・アルダー反応によって形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応が進行して前記共役ジエン構造と前記ジエノフィル構造が生成されるディールス・アルダー反応付加部を有し、かつ、シロキサン構造を有する化合物である<1>に記載の組成物。
<3> 前記化合物(X)が、ジエノフィル構造を有し、かつ、シロキサン構造を有する化合物(A)と、共役ジエン構造を有する化合物(B)とのディールス・アルダー反応により形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応を介して前記共役ジエン構造を有する化合物(B)を放出する化合物である、<2>に記載の組成物。
<4> 前記シロキサン構造を有する化合物(A)が、m個のRSi(O0.5)3ユニット(mは8~16の整数を表し、Rは、それぞれ独立に、水素原子または置換基を表す。)を有し、各ユニットが各ユニットにおける酸素原子を共有して他のユニットに連結しカゴ構造を形成している化合物(I)またはその重合体である、<3>に記載の組成物。
<5> 前記化合物(I)が、下記一般式(Q-1)~(Q-7)のいずれかで表される化合物である、<4>に記載の組成物。
<6> 前記共役ジエン構造を有する化合物(B)が、一般式(B-1)~一般式(B-3)のいずれかで表される化合物である、<3>~<5>のいずれかに記載の組成物。
一般式(B-1)および一般式(B-2)中、Wは、-O-、-C(O)-、-C(O)O-、-S(O)-、-S(O)2-、-C(X17)(X18)-、または、-N(X19)-を表す。X17~X19は、それぞれ独立に、水素原子または置換基を表す。)
<7> 前記化合物(X)中における前記共役ジエン構造を有する化合物(B)の付加量が、前記化合物(X)全量に対して、5~80質量%である<3>~<6>のいずれかに記載の組成物。
<8> さらに、溶剤を含む<1>~<7>のいずれかに記載の組成物。
<9> 絶縁膜形成用途に用いられる<1>~<8>のいずれかに記載の組成物。
<10> <1>~<9>のいずれかに記載の組成物を基板上に塗布した後、硬膜することを特徴とする絶縁膜の製造方法。
<11> <10>に記載の製造方法を用いて製造された絶縁膜。
<12> <11>に記載の絶縁膜を用いて製造された電子デバイス。
<13> 加熱、光照射、放射線照射またはそれらの組み合わせにより、その一部が脱離して揮発性成分を生じ、残部に不飽和基を生成する官能基を有する化合物。
<14> 共役ジエン構造とジエノフィル構造とのディールス・アルダー反応によって形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応が進行して前記共役ジエン構造と前記ジエノフィル構造が生成されるディールス・アルダー反応付加部を有し、かつ、シロキサン構造を有する樹脂。
<15> ジエノフィル構造を有し、かつ、シロキサン構造を有する化合物(A)と、共役ジエン構造を有する化合物(B)とのディールス・アルダー反応により形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応を介して前記共役ジエン構造を有する化合物(B)を放出する樹脂。
<16> 一般式(Q-1)~(Q-7)のいずれかで表される化合物またはその重合体と、一般式(B-1)~(B-3)のいずれかで表される化合物とのディールス・アルダー反応により形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応を介して前記一般式(B-1)~(B-3)のいずれかで表される化合物を放出する樹脂。
一般式(B-1)および一般式(B-2)中、Wは、-O-、-C(O)-、-C(O)O-、-S(O)-、-S(O)2-、-C(X17)(X18)-、または、-N(X19)-を表す。X17~X19は、それぞれ独立に、水素原子または置換基を表す。) It has been found that the above object of the present invention can be achieved by the following means.
<1> A composition containing a compound (X) having a functional group that partially generates a volatile component by heating, light irradiation, radiation irradiation, or a combination thereof to generate a volatile component, and generates an unsaturated group in the remainder. .
<2> The compound (X) is formed by a Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation, or a combination thereof, and the conjugated diene The composition according to <1>, which is a compound having a Diels-Alder reaction addition part for generating a structure and the dienophile structure and having a siloxane structure.
<3> The compound (X) is formed by a Diels-Alder reaction between a compound (A) having a dienophile structure and having a siloxane structure and a compound (B) having a conjugated diene structure. <2> The composition according to <2>, which is a compound that releases the compound (B) having the conjugated diene structure through reverse Diels-Alder reaction by irradiation, irradiation, or a combination thereof.
<4> The compound (A) having the siloxane structure is m RSi (O 0.5 ) 3 units (m represents an integer of 8 to 16, and R independently represents a hydrogen atom or a substituent. The composition according to <3>, wherein each unit is a compound (I) or a polymer thereof in which each unit shares an oxygen atom in each unit and is linked to another unit to form a cage structure.
<5> The composition according to <4>, wherein the compound (I) is a compound represented by any one of the following general formulas (Q-1) to (Q-7).
<6> Any of <3> to <5>, wherein the compound (B) having a conjugated diene structure is a compound represented by any one of the general formulas (B-1) to (B-3) A composition according to claim 1.
In the general formulas (B-1) and (B-2), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (X 17 ) (X 18 ) —, or —N (X 19 ) —. X 17 to X 19 each independently represents a hydrogen atom or a substituent. )
<7> The amount of the compound (B) having the conjugated diene structure in the compound (X) is 5 to 80% by mass with respect to the total amount of the compound (X). <3> to <6> A composition according to any one of the above.
<8> The composition according to any one of <1> to <7>, further comprising a solvent.
<9> The composition according to any one of <1> to <8>, which is used for insulating film formation.
<10> A method for producing an insulating film, comprising applying the composition according to any one of <1> to <9> onto a substrate and then hardening the composition.
<11> An insulating film manufactured using the manufacturing method according to <10>.
<12> An electronic device manufactured using the insulating film according to <11>.
<13> A compound having a functional group that is partially desorbed by heating, light irradiation, radiation irradiation, or a combination thereof to generate a volatile component, and the remainder generates an unsaturated group.
<14> Formed by the Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation, or a combination thereof to produce the conjugated diene structure and the dienophile structure. A resin having a Diels-Alder reaction addition portion and a siloxane structure.
<15> Formed by Diels-Alder reaction of a compound (A) having a dienophile structure and having a siloxane structure and a compound (B) having a conjugated diene structure. Resin which releases the compound (B) having the conjugated diene structure through reverse Diels-Alder reaction in combination.
<16> A compound represented by any one of the general formulas (Q-1) to (Q-7) or a polymer thereof, and any one represented by any one of the general formulas (B-1) to (B-3) Formed by a Diels-Alder reaction with a compound and represented by any one of the general formulas (B-1) to (B-3) via a reverse Diels-Alder reaction by heating, light irradiation, radiation irradiation or a combination thereof. A resin that releases the compound.
In the general formulas (B-1) and (B-2), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2- , -C (X 17 ) (X 18 )-, or -N (X 19 )-. X 17 to X 19 each independently represents a hydrogen atom or a substituent. )
本発明の組成物には、加熱、光照射、放射線照射またはそれらの組み合わせにより、その一部が脱離して揮発性成分を生じ、残部に不飽和基を生成する官能基を有する化合物(X)が含まれる。まず、化合物(X)について詳述する。 Hereinafter, the composition of the present invention and the insulating film obtained from the composition will be described in detail.
In the composition of the present invention, the compound (X) having a functional group that is partially removed by heating, light irradiation, radiation irradiation, or a combination thereof to generate a volatile component, and the remainder generates an unsaturated group. Is included. First, the compound (X) will be described in detail.
化合物(X)は、加熱、光照射、放射線照射またはそれらの組み合わせにより、その一部が脱離して揮発性成分を生じ、残部に不飽和基を生成する官能基を有する。
化合物(X)を含む組成物は、後述するように種々の用途に用いることができる。特に、化合物(X)を含む組成物を用いて膜の製造を行うと、硬膜時に行われる加熱処理や光照射や放射線照射などの高エネルギー線照射処理の際に、官能基から揮発性成分の脱離が進行する。揮発性成分が生じることにより、膜中に空孔が形成される。さらに、官能基の残部に不飽和基が生じ、残基間で硬化反応が生ずるため、低誘電率、高屈折率、高機械強度、高耐熱性、高酸化ストレス耐性を示し、誘電率が長期安定な膜が形成できる。
なお、加熱条件、光照射、放射線照射条件などは、使用される化合物(X)の構造によって最適な条件は変化する。なお、通常、後述する膜形成時の加熱処理または高エネルギー線照射の条件において、揮発性成分の脱離反応が良好に進行する。 <Compound (X)>
The compound (X) has a functional group that generates a volatile component by removing a part thereof by heating, light irradiation, radiation irradiation, or a combination thereof, and generates an unsaturated group in the remainder.
The composition containing compound (X) can be used for various applications as described later. In particular, when a film is produced using a composition containing compound (X), a volatile component is removed from a functional group during a high-energy ray irradiation treatment such as heat treatment or light irradiation or radiation irradiation performed during hardening. Desorption proceeds. Due to the generation of volatile components, voids are formed in the film. In addition, unsaturated groups are formed in the remainder of the functional group, and a curing reaction occurs between the residues. Therefore, it exhibits low dielectric constant, high refractive index, high mechanical strength, high heat resistance, and high oxidative stress resistance, and has a long dielectric constant. A stable film can be formed.
Note that the optimum conditions for the heating conditions, light irradiation, radiation irradiation conditions, and the like vary depending on the structure of the compound (X) used. Normally, the desorption reaction of volatile components proceeds well under the conditions of heat treatment during film formation described later or irradiation with high energy rays.
この官能基の具体例としては、以下のような(G-1)~(G-7)などの官能基や、後述するディールス・アルダー反応付加部などが挙げられる。 A part of the functional group of the compound (X) is removed by heating, light irradiation, radiation irradiation or a combination thereof to generate a volatile component, and an unsaturated group is generated in the remainder. Such a functional group is not particularly limited, but includes a group containing a dithiocarboxylic acid ester, a group containing a thioester, a group containing an ester, a group containing an azo group, a group containing a carbon-carbon double bond, and a sulfonic acid ester. A group containing a carbamate group, a group containing a carbonate group, a group containing a silicon atom, and the like.
Specific examples of this functional group include the following functional groups such as (G-1) to (G-7), and a Diels-Alder reaction addition unit described later.
炭化水素基としては、例えば、飽和炭化水素基(例えば、アルキル基)や芳香族炭化水素基(例えば、ベンゼン基)などが挙げられる。なお、*は結合位置を表す。 In (G-1) and (G-3), R 30 represents a hydrocarbon group.
Examples of the hydrocarbon group include a saturated hydrocarbon group (for example, an alkyl group) and an aromatic hydrocarbon group (for example, a benzene group). Note that * represents a bonding position.
(G-1)中、Lは、2価の連結基を表す。2価の連結基としては、例えば、置換または無置換の炭素数1~20のアルキレン基(例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、イソプロピレン基など)、置換または無置換のアリーレン基(例えば、o-フェニレン基、m-フェニレン基、p-フェニレン基、1,4-ナフチレン基など)などが挙げられる。
(G-2)中、Yは、それぞれ独立に、アルキル基、アルケニル基、ケイ素原子含有基、シクロアルキル基、またはアリール基を表す。複数のYは、同一であっても異なっていてもよい。Lは、2価の連結基を表す。連結基の具体例は、上記と同様である。
なお、ケイ素原子含有基は、後述するRで表されるケイ素原子含有基と同義である。 In (G-1), X represents S, O, Se, or Te (preferably S or O). Two Xs in (G-1) may be the same or different.
In (G-1), L represents a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, propylene group, butylene group, isopropylene group), substituted or unsubstituted arylene. Groups (for example, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, etc.) and the like.
In (G-2), each Y independently represents an alkyl group, an alkenyl group, a silicon atom-containing group, a cycloalkyl group, or an aryl group. A plurality of Y may be the same or different. L represents a divalent linking group. Specific examples of the linking group are the same as described above.
In addition, a silicon atom containing group is synonymous with the silicon atom containing group represented by R mentioned later.
また、残部として生じる不飽和基としては、特に限定されず、炭素-炭素二重結合または炭素-炭素三重結合を含む基であればよい。例えば、アルケニル基(炭素数1~6が好ましく、さらに炭素数1~2が好ましい。具体的には、ビニル基、アリル基)、アルキニル基(炭素数1~6が好ましく、さらに炭素数1~2が好ましい。具体的には、エチニル基)などが好ましく挙げられる。
このような不飽和基が生じることにより、硬膜時に不飽和基間で架橋反応が進行し、優れた機械的強度を示す膜を得ることができる。 The volatile component generated by desorption from the functional group is not particularly limited, and varies depending on the structure of the functional group. For example, dithiocarboxylic acid, thioester, thiol, ester, nitrogen molecule, amine, alkane, alkene, alkyne, alcohol, sulfonic acid, silane, silanol, carbon dioxide and the like.
Further, the unsaturated group generated as the remainder is not particularly limited, and may be a group containing a carbon-carbon double bond or a carbon-carbon triple bond. For example, an alkenyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms, more preferably a vinyl group or an allyl group), an alkynyl group (preferably having 1 to 6 carbon atoms, and further having 1 to 6 carbon atoms). The ethynyl group is preferred.
When such an unsaturated group is generated, a crosslinking reaction proceeds between the unsaturated groups at the time of hardening, and a film exhibiting excellent mechanical strength can be obtained.
化合物(X)としては、耐熱性に優れる点で、ポリアリーレンエーテル、ポリベンゾオキサゾール、シロキサン構造(Si-O結合)を有する化合物またはその重合体、アダマンタン、ビアダマンタン、ジアマンタン、トリアマンタン、テトラマンタン、およびドデカヘドランからなる群から選ばれるカゴ型構造を有する化合物またはその重合体が挙げられる。なかでも、シロキサン構造(Si-O結合)を有する化合物またはその重合体が好ましい。 The compound (X) may be a low molecular compound or a high molecular compound (for example, a resin), and the structure thereof is not particularly limited. For example, in the case of a polymer compound, the main skeleton includes polyimide, polyurethane, polyethylene, polyester, polyphenylene ether, polybenzoxazole, polyarylene ether, siloxane structure (Si—O bond), cage structure, diamondoid structure, Examples include diamondoid-arylene structures.
As the compound (X), polyarylene ether, polybenzoxazole, a compound having a siloxane structure (Si—O bond) or a polymer thereof, adamantane, biadamantane, diamantane, triamantane, tetramantane in view of excellent heat resistance And a compound having a cage structure selected from the group consisting of dodecahedrane or a polymer thereof. Among these, a compound having a siloxane structure (Si—O bond) or a polymer thereof is preferable.
また、化合物の主骨格がポリベンゾオキサゾールである化合物(X)は、ベンゾオキサゾール前駆体を利用する国際公開第2005-019305号パンフレットを参照して合成することができる。 Compound (X) in which the main skeleton of the compound is polyarylene ether can be synthesized, for example, with reference to JP-T-2003-520864.
The compound (X) in which the main skeleton of the compound is polybenzoxazole can be synthesized with reference to International Publication No. 2005-019305 pamphlet using a benzoxazole precursor.
なお、上述した残部に不飽和基を生成する官能基は、一般式(H-1)~一般式(H-6)のいずれかで表される化合物またはその重合体中のいずれの部分に結合していてもよい。 In general formula (H-1) to general formula (H-6), V 1 to V 8 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, silyl group, acyl group, alkoxy group. Represents a carbonyl group or a carbamoyl group. Z 1 to Z 8 each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group. m 1 and m 5 each independently represents an integer of 1 to 16 (preferably 1 to 3, more preferably 2). n 1 and n 5 each independently represents an integer of 0 to 15 (preferably 0 or 1). m 2 , m 3 , m 6 and m 7 each independently represents an integer of 1 to 15 (preferably 1 to 3, more preferably 2). n 2 , n 3 , n 6 , and n 7 each independently represents an integer of 0 to 14 (preferably 0 or 1). m 4 and m 8 each independently represents an integer of 1 to 20 (preferably 1 to 3, more preferably 2). n 4 and n 8 each independently represents an integer of 0 to 19 (preferably 0 or 1).
The functional group that generates an unsaturated group in the remainder is bonded to any part of the compound represented by the general formula (H-1) to the general formula (H-6) or a polymer thereof. You may do it.
上記化合物(X)の好適な実施態様の一つとして、共役ジエン構造とジエノフィル構造とのディールス・アルダー反応によって形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応が進行して共役ジエン構造とジエノフィル構造が生成されるディールス・アルダー反応付加部を有し、かつ、シロキサン構造を有する化合物(Y)が挙げられる。まず、化合物(Y)について詳述する。 <Compound (Y)>
As one of the preferred embodiments of the above compound (X), it is formed by Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof. Examples thereof include a compound (Y) having a Diels-Alder reaction addition part for producing a conjugated diene structure and a dienophile structure and having a siloxane structure. First, the compound (Y) will be described in detail.
化合物(Y)を含む組成物は、後述するように種々の用途に用いることができる。特に、化合物(Y)を含む組成物を用いて膜の製造を行うと、硬膜時に行われる加熱処理や光照射や放射線照射などの高エネルギー線照射処理の際に、逆ディールス・アルダー反応が進行する。その際、ディールス・アルダー反応付加部が共役ジエン構造とジエノフィル構造とに解離し、一方または両方が揮発して膜空隙が増大する。更に、残基間で硬化反応が生ずるため、低誘電率、高屈折率、高機械強度、高耐熱性、高酸化ストレス耐性を示し、誘電率が長期安定な膜が形成できる。 Compound (Y) is a compound having a Diels-Alder reaction addition part and having a siloxane structure. In the present invention, the Diels-Alder reaction addition part is a site having a ring structure formed by a Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and is reversed by heating, light irradiation, radiation irradiation or a combination thereof. The Diels-Alder reaction proceeds to produce a conjugated diene structure and a dienophile structure.
The composition containing the compound (Y) can be used for various applications as described later. In particular, when a film is produced using a composition containing the compound (Y), a reverse Diels-Alder reaction occurs during high energy ray irradiation treatment such as heat treatment or light irradiation or radiation irradiation performed at the time of hardening. proceed. At that time, the Diels-Alder reaction addition part dissociates into a conjugated diene structure and a dienophile structure, and one or both volatilizes to increase the film gap. Furthermore, since a curing reaction occurs between the residues, a film having a low dielectric constant, a high refractive index, a high mechanical strength, a high heat resistance, a high oxidative stress resistance and a long-term dielectric constant can be formed.
ディールス・アルダー反応付加部を形成する共役ジエン構造は、特に限定されず、鎖状共役ジエン構造、および環状共役ジエン構造を用いることができる。共役ジエン構造の好適な例としては、例えば、以下のような構造が挙げられる。 <Conjugated diene structure>
The conjugated diene structure forming the Diels-Alder reaction addition part is not particularly limited, and a chain conjugated diene structure and a cyclic conjugated diene structure can be used. Preferable examples of the conjugated diene structure include the following structures.
なお、(D-1)~(D-17)骨格中、Y1~Y10は、それぞれ独立に、水素原子また置換基を表す。置換基の定義は、後述する一般式(F-1)~一般式(F-4)中の置換基と同義である。 Among them, a cyclic conjugated diene structure is preferable because of its excellent stability against heat and the like, and in particular, the (D-1) skeleton, the (D-2) skeleton, the (D-8) skeleton, the (D-9) skeleton, D-10) skeleton, (D-11) skeleton and the like are preferable.
In the (D-1) to (D-17) skeletons, Y 1 to Y 10 each independently represents a hydrogen atom or a substituent. The definition of the substituent is the same as the substituent in formulas (F-1) to (F-4) described later.
ディールス・アルダー反応付加部を形成するジエノフィル構造は、上記の共役ジエン構造と付加的に反応して環式構造を与える不飽和構造であれば特に限定されず、炭素-炭素二重結合を有するアルケニル基や、炭素-炭素三重結合を有するアルキニル基などが挙げられる。ジエノフィル構造の好適な例としては、例えば、以下のような構造が挙げられる。なかでも、(E-1)骨格、(E-2)骨格、(E-3)骨格などが好ましい。 <Dienophile structure>
The dienophile structure forming the Diels-Alder reaction adduct is not particularly limited as long as it is an unsaturated structure that additionally reacts with the above conjugated diene structure to give a cyclic structure, and the alkenyl having a carbon-carbon double bond And alkynyl groups having a carbon-carbon triple bond. Preferable examples of the dienophile structure include the following structures. Of these, (E-1) skeleton, (E-2) skeleton, (E-3) skeleton and the like are preferable.
本発明におけるディールス・アルダー反応付加部は、上記共役ジエン構造とジエノフィル構造との付加反応により得られる付加部であり、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応が進行して共役ジエン構造とジエノフィル構造が生成される。
なお、加熱条件、光照射、放射線照射条件などは、使用される化合物によって最適な条件は変化する。なお、通常、後述する膜形成時の加熱処理または高エネルギー線照射の条件において、逆ディールス・アルダー反応が進行する。 <Diels Alder reaction addition part>
The Diels-Alder reaction addition portion in the present invention is an addition portion obtained by the addition reaction of the conjugated diene structure and the dienophile structure, and the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof. Thus, a conjugated diene structure and a dienophile structure are generated.
Note that the optimum conditions such as heating conditions, light irradiation, and radiation irradiation conditions vary depending on the compounds used. In general, the reverse Diels-Alder reaction proceeds under the conditions of heat treatment or high energy ray irradiation during film formation described below.
一般式(F-2)~一般式(F-4)中、Wは、-O-、-C(O)-、-C(O)O-、-S(O)-、-S(O)2-、-C(Y12)(Y13)-、または、-N(Y14)-を表す。Y12~Y14は、それぞれ独立に、水素原子または置換基を表す。
一般式(F-1)~一般式(F-4)中、*は化合物(Y)との結合位置を表す。) (In general formula (F-1) to general formula (F-4), Y 1 to Y 11 each represents a hydrogen atom or a substituent.
In the general formulas (F-2) to (F-4), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (Y 12 ) (Y 13 ) —, or —N (Y 14 ) —. Y 12 to Y 14 each independently represents a hydrogen atom or a substituent.
In the general formulas (F-1) to (F-4), * represents a bonding position with the compound (Y). )
なお、上記各基は、後述するRで表される各基と同義である。 In general formula (F-1) to general formula (F-4), Y 1 to Y 11 each represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, or a group obtained by combining them. Of these, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a silicon atom-containing group are preferable.
In addition, said each group is synonymous with each group represented by R mentioned later.
Y12~Y14は、それぞれ独立に、水素原子または置換基を表す。Y12~Y14で表される置換基の定義は、Y1~Y11で表される置換基の定義と同義である。なかでも、アルキル基、シクロアルキル基が好ましい。 In the general formulas (F-2) to (F-4), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (Y 12 ) (Y 13 ) —, or —N (Y 14 ) —. Of these, —O—, —C (O) —, and —C (Y 12 ) (Y 13 ) — are preferable.
Y 12 to Y 14 each independently represents a hydrogen atom or a substituent. The definition of the substituent represented by Y 12 to Y 14 is the same as the definition of the substituent represented by Y 1 to Y 11 . Of these, an alkyl group and a cycloalkyl group are preferable.
化合物(Y)は、シロキサン構造(Si-O結合)をもつ化合物であり、低分子化合物および高分子化合物(例えば、樹脂)を含む。本発明の効果を損なわない限り、いかなるシロキサン構造を有する化合物であってもよい。ケイ素原子と酸素原子とでなるシロキサン構造を有する化合物(Y)は、優れた耐熱性を示す。化合物(Y)中におけるシロキサン構造の含有量としては、化合物(Y)全量に対して、30~100質量%が好ましく、60~100質量%がより好ましい。 <Siloxane structure>
The compound (Y) is a compound having a siloxane structure (Si—O bond), and includes a low molecular compound and a high molecular compound (for example, a resin). A compound having any siloxane structure may be used as long as the effects of the present invention are not impaired. The compound (Y) having a siloxane structure composed of silicon atoms and oxygen atoms exhibits excellent heat resistance. The content of the siloxane structure in the compound (Y) is preferably 30 to 100% by mass and more preferably 60 to 100% by mass with respect to the total amount of the compound (Y).
より好ましくは、m個のRSi(O0.5)3ユニットが、その酸素原子を共有しながら他のRSi(O0.5)3ユニットと互いに連結することで形成されるカゴ型シルセスキオキサン、およびそれを繰り返し単位とする重合体等が挙げられる。なお、mは8~16の整数を表す。Rは、それぞれ独立して、水素原子または置換基を表し、少なくとも一つがディールス・アルダー反応付加部を表すことが好ましい。 As a preferred embodiment of the above silsesquioxane compound, cage-type silsesquioxane or a polymer thereof can be mentioned from the viewpoint of excellent heat resistance.
More preferably, m pieces of RSi (O 0.5) 3 units, other RSi (O 0.5) 3 units and cage silsesquioxane is formed by concatenating each other while sharing the oxygen atoms, and it And the like. Note that m represents an integer of 8 to 16. Each R independently represents a hydrogen atom or a substituent, and preferably at least one represents a Diels-Alder reaction addition part.
*-L1-Si-(R20)3 (2) The silicon atom-containing group represented by R is not particularly limited as long as silicon is contained, but a group represented by the general formula (2) is preferable.
* -L 1 -Si- (R 20 ) 3 (2)
アルキレン基としては、炭素数1~12が好ましく、炭素数1~6がより好ましい。R21、R22、R23およびR20は、それぞれ独立にアルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、アルコキシ基を表す。R21、R22、R23およびR20で表されるアルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、アルコキシ基の定義は、上述のRの定義と同じであり、好ましくはメチル基、エチル基、ブチル基、シクロヘキシル基、ビニル基、エチニル基などが挙げられる。Rとしてのケイ素原子含有基としては、シリルオキシ基(トリメチルシリルオキシ、トリエチルシリルオキシ、t-ブチルジメチルシリルオキシ)がもっとも好ましい。 In general formula (2), * represents a bonding position with a silicon atom. L 1 represents an alkylene group, —O—, —S—, —Si (R 21 ) (R 22 ) —, —N (R 23 ) —, or a divalent linking group obtained by combining these. L 1 is preferably an alkylene group, —O—, or a divalent linking group in combination of these.
The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. R 21 , R 22 , R 23 and R 20 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or an alkoxy group. The definitions of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group and alkoxy group represented by R 21 , R 22 , R 23 and R 20 are the same as those defined above for R, preferably methyl Group, ethyl group, butyl group, cyclohexyl group, vinyl group, ethynyl group and the like. The silicon atom-containing group as R is most preferably a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy).
(R40)4-n-Si-(X)n 一般式(K)
上記一般式(K)中、R40は一般式(F-1)~一般式(F-4)で表されるディールス・アルダー反応付加部を表す。Xは、アルコキシ基またはハロゲン元素(例えば、塩素原子)を表す。nは1~3の整数を表す。
なお、一般式(K)で表されるシランカップリング剤の加水分解反応は、加熱などの公知の方法により行うことができる。 As another preferable embodiment of the compound (Y), the above-mentioned silane coupling agent having a Diels-Alder reaction addition part, or a hydrolysis condensate thereof can be mentioned. More preferably, the silane coupling agent represented by the following formula | equation, or its hydrolysis-condensation product is mentioned.
(R 40 ) 4-n —Si— (X) n General formula (K)
In the general formula (K), R 40 represents a Diels-Alder reaction addition part represented by the general formula (F-1) to the general formula (F-4). X represents an alkoxy group or a halogen element (for example, a chlorine atom). n represents an integer of 1 to 3.
The hydrolysis reaction of the silane coupling agent represented by the general formula (K) can be performed by a known method such as heating.
化合物(Y)が高分子化合物の場合、その重量平均分子量(Mw)は、2.5×104~75×104であることが好ましく、3.5×104~35×104であることがより好ましく、4.5×104~25×104であることが最も好ましい。
化合物(Y)が高分子化合物の場合、その数平均分子量(Mn)は、1.5×104~35×104であることが好ましく、1.5×104~20×104であることがより好ましく、2.5×104~15×104であることが最も好ましい。
化合物(Y)が高分子化合物の場合、そのZ+1平均分子量(MZ+1)は、1.5×104~65×104であることが好ましく、2.5×104~50×104であることがより好ましく、3.5×104~35×104であることが最も好ましい。
上記範囲の重量平均分子量および数平均分子量に設定することにより、有機溶剤に対する溶解性およびフィルターろ過性が向上し、保存時のパーティクルの発生が抑制でき、塗布膜の面状が改善された、低誘電率である膜を形成することができる。 The molecular weight of the compound (Y) is not particularly limited, and may be a low molecular compound or a high molecular compound (for example, a resin).
When the compound (Y) is a polymer compound, its weight average molecular weight (M w ) is preferably 2.5 × 10 4 to 75 × 10 4 , and is 3.5 × 10 4 to 35 × 10 4 . More preferably, it is most preferably 4.5 × 10 4 to 25 × 10 4 .
When the compound (Y) is a polymer compound, its number average molecular weight (M n ) is preferably 1.5 × 10 4 to 35 × 10 4 , and is 1.5 × 10 4 to 20 × 10 4 . More preferably, it is 2.5 × 10 4 to 15 × 10 4 .
When the compound (Y) is a polymer compound, the Z + 1 average molecular weight (M Z + 1 ) is preferably 1.5 × 10 4 to 65 × 10 4 , and is 2.5 × 10 4 to 50 × 10 4 . More preferably, it is most preferably 3.5 × 10 4 to 35 × 10 4 .
By setting the weight average molecular weight and number average molecular weight within the above ranges, solubility in organic solvents and filter filterability are improved, generation of particles during storage can be suppressed, and the surface state of the coating film is improved. A film having a dielectric constant can be formed.
化合物(Y)の製造方法は、特に限定されないが、以下の2つの態様が好ましい。
(1)ジエノフィル構造を有し、かつ、シロキサン構造を有する化合物と、共役ジエン構造を有する化合物とのディールス・アルダー反応により形成される化合物(Y)
(2)共役ジエン構造を有し、かつ、シロキサン構造を有する化合物と、ジエノフィル構造を有する化合物とのディールス・アルダー反応により形成される化合物(Y)
なかでも、合成が容易であり、後述する用途に好適に使用できる点で、(1)の態様がより好ましい。
以下に、(1)の態様で使用されるジエノフィル構造を有し、かつ、シロキサン構造を有する化合物(A)と、共役ジエン構造を有する化合物(B)について詳述する。 <Manufacturing method>
Although the manufacturing method of a compound (Y) is not specifically limited, The following two aspects are preferable.
(1) Compound (Y) formed by Diels-Alder reaction between a compound having a dienophile structure and a siloxane structure and a compound having a conjugated diene structure
(2) Compound (Y) formed by Diels-Alder reaction between a compound having a conjugated diene structure and having a siloxane structure and a compound having a dienophile structure
Especially, the aspect of (1) is more preferable at the point which is easy to synthesize | combine and can be used conveniently for the use mentioned later.
Hereinafter, the compound (A) having a dienophile structure and having a siloxane structure and the compound (B) having a conjugated diene structure used in the embodiment of (1) will be described in detail.
化合物(A)とは、ジエノフィル構造を有し、かつ、シロキサン構造を有する化合物である。
ジエノフィル構造は上述のように共役ジエン構造と付加的に反応して環式構造を与える不飽和構造であり、その構造は特に制限されず、上記に例示した構造などが挙げられる。なかでも、アルケニル基、アルキニル基が好ましく挙げられる。 <Compound (A)>
The compound (A) is a compound having a dienophile structure and a siloxane structure.
As described above, the dienophile structure is an unsaturated structure that additionally reacts with the conjugated diene structure to give a cyclic structure. The structure is not particularly limited, and examples include the structures exemplified above. Of these, an alkenyl group and an alkynyl group are preferable.
(R1)3-Si-O- (II)
〔MO-Si(O0.5)3〕m (III)
(R1)3-Si-Cl (IV) It is also preferred that R in the compound (I) of the present invention is a group represented by the following general formula (II). In this case, the group represented by the general formula (II) can be synthesized by reacting a compound represented by the following general formula (III) with a compound represented by the following general formula (IV).
(R 1 ) 3 —Si—O— (II)
[MO-Si (O 0.5 ) 3 ] m (III)
(R 1 ) 3 —Si—Cl (IV)
溶媒としては、トルエン、ヘキサン、テトラヒドロフラン(THF)などの有機溶剤が好ましい。
一般式(III)で表される化合物と一般式(IV)で表される化合物を反応させる際には、トリエチルアミン、ピリジンなどの塩基を添加してもよい。 The reaction between the compound represented by the general formula (III) and the compound represented by the general formula (IV) is carried out, for example, in a solvent by combining the compound represented by the general formula (III) and the general formula (III) The compound represented by the general formula (IV) is added in an amount of 1 to 100 times the number of Si-OM groups contained in the compound represented by general formula (IV), and the stirring is usually performed at 0 to 180 ° C. for 10 minutes to 20 hours. .
As the solvent, organic solvents such as toluene, hexane, and tetrahydrofuran (THF) are preferable.
When the compound represented by the general formula (III) and the compound represented by the general formula (IV) are reacted, a base such as triethylamine or pyridine may be added.
シロキサン構造を有する化合物(A)の好適な実施態様の一つとしては、化合物(I)を繰り返し単位とする重合体が挙げられ、複数の異なった化合物(I)の重合物が含まれていてもよい。その場合、複数の異なった化合物(I)からなる共重合体であってもよいし、ホモポリマーの混合物であってもよい。本発明の組成物が、複数の異なった化合物(I)からなる共重合体を含む場合、m=8、10、および12から選ばれる2種以上の化合物(I)の混合物の共重合体であることが好ましい。 <Polymer>
One preferred embodiment of the compound (A) having a siloxane structure includes a polymer having the compound (I) as a repeating unit, and includes a polymer of a plurality of different compounds (I). Also good. In that case, the copolymer which consists of several different compound (I) may be sufficient, and the mixture of a homopolymer may be sufficient. When the composition of the present invention contains a copolymer composed of a plurality of different compounds (I), it is a copolymer of a mixture of two or more compounds (I) selected from m = 8, 10, and 12. Preferably there is.
この場合、化合物(I)由来の成分は、共重合物中の50質量%以上であることが好ましく、70質量%以上であることが最も好ましい。
化合物(I)を繰り返し単位とする重合体を製造した際に含まれる未反応の化合物(I)の含量は、全固形分に対して、15質量%以下が好ましく、さらに好ましくは10質量%以下であり、最も好ましくは7質量%以下である。これにより塗布面状が改善できる。なお、全固形分とは、化合物(I)の重合体と未反応物との合計成分を意味する。 The compound (A) having a siloxane structure may be a copolymer with a compound other than the compound (I). The compound used in that case is preferably a compound having a plurality of polymerizable carbon-carbon unsaturated bonds or SiH groups. Examples of preferred compounds include vinyl silanes, vinyl siloxanes, phenylacetylenes, vinyl adamantanes, [(HSiO 0.5 ) 3 ] 8 and the like.
In this case, the component derived from the compound (I) is preferably 50% by mass or more, and most preferably 70% by mass or more in the copolymer.
The content of the unreacted compound (I) contained in the production of the polymer having the compound (I) as a repeating unit is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total solid content. And most preferably 7% by mass or less. Thereby, the coated surface state can be improved. The total solid content means a total component of the polymer of compound (I) and an unreacted product.
シロキサン構造を有する化合物(A)の数平均分子量(Mn)は、化合物(I)単量体を除いて、1.0×104~30×104であることが好ましく、1.0×104~15×104であることがより好ましく、2.0×104~10×104であることが最も好ましい。
シロキサン構造を有する化合物(A)のZ+1平均分子量(MZ+1)は、化合物(I)単量体を除いて、1.0×104~60×104であることが好ましく、2.0×104~45×104であることがより好ましく、3.0×104~30×104であることが最も好ましい。
上記範囲の重量平均分子量および数平均分子量に設定することにより、有機溶剤に対する溶解性およびフィルターろ過性が向上し、塗布膜の面状が改善された、低誘電率である膜を形成することができる。 The weight average molecular weight (M w ) of the compound (A) having a siloxane structure is preferably 2.0 × 10 4 to 70 × 10 4 excluding the compound (I) monomer, It is more preferably 10 4 to 30 × 10 4 , and most preferably 4.0 × 10 4 to 20 × 10 4 .
The number average molecular weight (M n ) of the compound (A) having a siloxane structure is preferably 1.0 × 10 4 to 30 × 10 4 excluding the compound (I) monomer, It is more preferably 10 4 to 15 × 10 4 , and most preferably 2.0 × 10 4 to 10 × 10 4 .
The Z + 1 average molecular weight (M Z + 1 ) of the compound (A) having a siloxane structure is preferably 1.0 × 10 4 to 60 × 10 4 except for the compound (I) monomer, and 2.0 × It is more preferably 10 4 to 45 × 10 4 , and most preferably 3.0 × 10 4 to 30 × 10 4 .
By setting the weight average molecular weight and number average molecular weight within the above ranges, solubility in organic solvents and filter filterability can be improved, and the surface state of the coating film can be improved, and a film having a low dielectric constant can be formed. it can.
化合物(I)の重合体には、重合開始剤、添加剤または重合溶媒が重合体全量に対して0.1~40質量%結合していてもよい。それらの含有量は、重合体全量に対して、0.1~20質量%が好ましく、0.1~10質量%が、より好ましく、0.1~5質量%が最も好ましい。
これらについては、組成物のNMRスペクトル等から定量することができる。 It is preferable that unreacted alkenyl group and alkynyl group derived from compound (I) remain in the polymer of compound (I). Among alkenyl groups and alkynyl groups derived from compound (I), 10 to 90 It is preferable that the mol% remains unreacted, 20 to 80 mol% is preferably left unreacted, and 30 to 70 mol% is most preferably left unreacted. If it is in the said range, the sclerosis | hardenability and mechanical strength of the film | membrane obtained will improve more.
In the polymer of compound (I), 0.1 to 40% by mass of a polymerization initiator, an additive or a polymerization solvent may be bonded to the total amount of the polymer. Their content is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 10% by mass, most preferably from 0.1 to 5% by mass, based on the total amount of the polymer.
About these, it can quantify from the NMR spectrum etc. of a composition.
化合物(I)の炭素-炭素不飽和結合の重合反応としてはどのような重合反応でもよいが、例えば、ラジカル重合、カチオン重合、アニオン重合、開環重合、重縮合、重付加、付加縮合、遷移金属触媒重合などが挙げられる。 As a method for producing a polymer of compound (I), a production method using a polymerization reaction of a carbon-carbon unsaturated bond of compound (I), a hydrosilylation reaction, a sol-gel reaction using an acid or base catalyst Is mentioned.
The polymerization reaction of the carbon-carbon unsaturated bond of compound (I) may be any polymerization reaction. For example, radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, transition Examples include metal catalyst polymerization.
ゾルゲル反応は、例えば、ゾル-ゲル法のナノテクノロジーへの応用(CMC、2005)、ゾル-ゲル法応用の展開(CMC、2008)に記載の方法が挙げられる。 The hydrosilylation reaction is performed, for example, by the compound of the present invention and a compound containing two or more SiH groups in the molecule (for example, bis (dimethylsilyl) ethane, 1,1,3,3-tetramethyldimethyl). Dissolve siloxane etc. in an organic solvent (eg toluene, xylene etc.) and add catalyst (eg Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex etc.) 20 It can be performed by a method such as heating at ˜200 ° C.
Examples of the sol-gel reaction include the methods described in the application of sol-gel method to nanotechnology (CMC, 2005) and the development of application of sol-gel method (CMC, 2008).
また、酸素による重合開始剤の不活性化を抑制するために不活性ガス雰囲気下(例えば窒素、アルゴン等)で反応させることが好ましい。反応時の酸素濃度は、好ましくは100ppm以下、より好ましくは50ppm以下、特に好ましくは20ppm以下である。 The reaction temperature of the polymerization reaction in the present invention is usually 0 ° C. to 200 ° C., preferably 40 ° C. to 170 ° C., more preferably 80 ° C. to 160 ° C.
Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
溶剤としては、例えば、水や、メタノール、エタノール、プロパノール、ブタノール等のアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、アセトフェノン等のケトン系溶剤、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸ペンチル、酢酸ヘキシル、プロピオン酸メチル、プロピオン酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、γ-ブチロラクトン、メチルベンゾエート等のエステル系溶剤、1,4-ジオキサン、ジイソプロピルエーテル、ジブチルエーテル、アニソール、テトラヒドロフラン、ジフェニルエーテル等のエーテル系溶剤、トルエン、キシレン、メシチレン、1,2,4,5-テトラメチルベンゼン、ペンタメチルベンゼン、イソプロピルベンゼン、1,4-ジイソプロピルベンゼン、t-ブチルベンゼン、1,4-ジ-t-ブチルベンゼン、1,3,5-トリエチルベンゼン、1,3,5-トリ-t-ブチルベンゼン、4-t-ブチル-オルトキシレン、1-メチルナフタレン、1,3,5-トリイソプロピルベンゼン等の芳香族炭化水素系溶剤、N-メチルピロリジノン、ジメチルアセトアミド等のアミド系溶剤、四塩化炭素、ジクロロメタン、クロロホルム、1,2-ジクロロエタン、クロロベンゼン、1,2-ジクロロベンゼン、クロロベンゼン、1,2,4-トリクロロベンゼン等のハロゲン系溶剤、ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶剤などが利用できる。
これらの中でより好ましい溶剤は、エステル系溶剤、エーテル系溶剤および芳香族炭化水素系溶剤であり、具体的には、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸ペンチル、酢酸ヘキシル、プロピオン酸メチル、プロピレングリコールモノメチルエーテルアセテート、テトラヒドロフラン、ジフェニルエーテル、アニソール、トルエン、キシレン、メシチレン、t-ブチルベンゼンが好ましく、特に好ましくは酢酸エチル、酢酸ブチル、ジフェニルエーテル、アニソール、メシチレン、t-ブチルベンゼンである。これらは単独でも2種以上を混合して用いてもよい。
反応時に重合開始剤を分解させるのに必要な温度まで反応液を加温できるために、溶剤の沸点は65℃以上であることが好ましい。 As the solvent used in the above polymerization reaction, any solvent can be used as long as it can dissolve the compound (I) at a necessary concentration and does not adversely affect the properties of the film formed from the obtained polymer. May be. In the following description, for example, an ester solvent is a solvent having an ester group in the molecule.
Examples of the solvent include water, alcohol solvents such as methanol, ethanol, propanol and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate. , Butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether acetate, γ-butyrolactone, methyl benzoate and other ester solvents, 1,4-dioxane, diisopropyl ether , Ether solvents such as dibutyl ether, anisole, tetrahydrofuran, diphenyl ether, toluene, xylene, mesitylene, 1,2 4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3 , 5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methylnaphthalene, aromatic hydrocarbon solvents such as 1,3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, etc. Amide solvents such as carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, chlorobenzene, 1,2,4-trichlorobenzene, hexane, heptane, octane, Aliphatic hydrocarbon solvents such as cyclohexane can be used.
Among these solvents, more preferred are ester solvents, ether solvents and aromatic hydrocarbon solvents, and specifically, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate, propion. Methyl acid, propylene glycol monomethyl ether acetate, tetrahydrofuran, diphenyl ether, anisole, toluene, xylene, mesitylene and t-butylbenzene are preferred, and ethyl acetate, butyl acetate, diphenyl ether, anisole, mesitylene and t-butylbenzene are particularly preferred. These may be used alone or in admixture of two or more.
The boiling point of the solvent is preferably 65 ° C. or higher so that the reaction solution can be heated to a temperature necessary for decomposing the polymerization initiator during the reaction.
重合開始剤としては、特に、有機過酸化物または有機アゾ系化合物が好ましく用いられる。
有機過酸化物としては、日本油脂株式会社より市販されているパーヘキサH等のケトンパーオキサイド類、パーヘキサTMH等のパーオキシケタール類、パーブチルH-69等のハイドロパーオキサイド類、パークミルD、パーブチルC、パーブチルD等のジアルキルパーオキサイド類、ナイパーBW等のジアシルパーオキサイド類、パーブチルZ、パーブチルL等のパーオキシエステル類、パーロイルTCP等のパーオキシジカーボネート、ジイソブチリルパーオキサイド、クミルパーオキシネオデカノエート、ジ‐n‐プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ‐sec-ブチルパーオキシジカーボネート、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、ジ(4-t-ブチルクロヘキシル)パーオキシジカーボネート、ジ(2-エチルヘキシル)パーオキシジカーボネート、t-ヘキシルパーオキシネオデカノエート、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシネオヘプタノエート、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシピバレート、ジ(3,5,5-トリメチルヘキサノイル)パーオキサイド、ジラウロイルパーオキサイド、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、ジコハク酸パーオキサイド、2,5-ジメチル-2,5-ジ(2-エチルヘキサノイルパーオキシ)ヘキサン、t-ヘキシルパーオキシ-2-エチルヘキサノエート、ジ(4-メチルベンゾイル)パーオキサイド、t-ブチルパーオキシ-2-エチルヘキサノエート、ジ(3-メチルベンゾイル)パーオキサイド、ベンゾイル(3-メチルベンゾイル)パーオキサイド、ジベンゾイルパーオキサイド、1,1-ジ(t-ブチルパーオキシ)-2-メチルシクロヘキサン、1,1-ジ(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン、1,1-ジ(t-ヘキシルパーオキシ)シクロヘキサン、1,1-ジ(t-ブチルパーオキシ)シクロヘキサン、2,2-ジ(4,4-ジ‐(t-ブチルパーオキシ)シクロヘキシル)プロパン、t-ヘキシルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシマレイン酸、t-ブチルパーオキシ‐3,5,5、-トリメチルヘキサノエート、t-ブチルパーオキシラウレート、t-ブチルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシ-2-エチルヘキシルモノカーボネート、t-ヘキシルパーオキシベンゾエート、2,5-ジメチル‐2,5-ジ(ベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシアセテート、2,2-ジ(t-ブチルパーオキシ)ブタン、t-ブチルパーオキシベンゾエート、n-ブチル-4,4-ジ-t-ブチルパーオキシバレレート、ジ(2-t-ブチルパーオキシイソプロピル)ベンゼン、ジクミルパーオキサイド、ジ‐t-ヘキシルパーオキサイド、2,5-ジメチル‐2,5-ジ(t-ブチルパーオキシ)ヘキサン、t-ブチルクミルパーイキサイド、ジ‐t-ブチルパーオキサイド、p-メタンヒドロパーオキサイド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン‐3、ジイソプロピルベンゼンヒドロパーオキサイド、1,1,3,3-テトラメチルブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、t-ブチルヒドロパーオキサイド、2,3-ジメチル-2,3-ジフェニルブタン、2,4-ジクロロベンゾイルパーオキサイド、o-クロロベンゾイルパーオキサイド、p-クロロベンゾイルパーオキサイド、トリス-(t-ブチルパーオキシ)トリアジン、2,4,4-トリメチルペンチルパーオキシネオデカノエート、α-クミルパーオキシネオデカノエート、t-アミルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシイソブチレート、ジ-t-ブチルパーオキシヘキサヒドロテレフタレート、ジ-t-ブチルパーオキシトリメチルアジペート、ジ-3-メトキシブチルパーオキシジカーボネート、ジ-イソプロピルパーオキシジカーボネート、t-ブチルパーオキシイソプロピルカーボネート、1,6-ビス(t-ブチルパーオキシカルボニルオキシ)ヘキサン、ジエチレングリコールビス(t-ブチルパーオキシカーボネート)、t-ヘキシルパーオキシネオデカノエート、アルケマ吉冨社より市販されているルペロックス11等が好ましく用いられる。
有機アゾ系化合物としては、和光純薬工業株式会社で市販されているV-30、V-40、V-59、V-60、V-65、V-70等のアゾニトリル化合物類、VA-080、VA-085、VA-086、VF-096、VAm-110、VAm-111等のアゾアミド化合物類、VA-044、VA-061等の環状アゾアミジン化合物類、V-50、VA-057等のアゾアミジン化合物類、V-601等のアゾエステル化合物類、2,2-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2-アゾビス(2,4-ジメチルバレロニトリル)、2,2-アゾビス(2-メチルプロピオニトリル)、2,2-アゾビス(2,4-ジメチルブチロニトリル)、1,1-アゾビス(シクロヘキサン-1-カーボニトリル)、1-〔(1-シアノ-1-メチルエチル)アゾ〕ホルムアミド、2,2-アゾビス{2-メチル-N-[1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル]プロピオンアミド}、2,2-アゾビス〔2-メチル-N-(2-ヒドロキシブチル)プロピオンアミド〕、2,2-アゾビス〔N-(2-プロペニル)-2-メチルプロピオンアミド〕、2,2-アゾビス(N-ブチル-2-メチルプロピオンアミド)、2,2-アゾビス(N-シクロヘキシル-2-メチルプロピオアミド)、2,2-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕ジヒドロクロリド、2,2-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕ジスルフェートジヒドレート、2,2-アゾビス{2-〔1-(2-ヒドロキシエチル)-2-イミダゾリン‐2-イル〕プロパン}ジヒドロクロリド、2,2-アゾビス〔2-〔2-イミダゾリン‐2-イル〕プロパン〕、2,2-アゾビス(1-イミノ-1-ピロリジノ-2-メチルプロパン)ジヒドロクロリド、2,2-アゾビス(2-メチルプロピオンアミジン)ジヒドロクロリド、2,2-アゾビス〔N-(2-カルボキシエチル)-2-メチルプロピオンアミジン〕テトラヒドレート、ジメチル2,2-アゾビス(2-メチルプロピオネート)、4,4-アゾビス(4-シアノバレリックアシッド)、2,2-アゾビス(2,4,4-トリメチルペンタン)等が好ましく用いられる。 The polymerization reaction of compound (I) is preferably performed in the presence of a nonmetallic polymerization initiator. For example, the polymerization can be carried out in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating.
As the polymerization initiator, an organic peroxide or an organic azo compound is particularly preferably used.
Examples of organic peroxides include ketone peroxides such as Perhexa H, peroxyketals such as Perhexa TMH, hydroperoxides such as Perbutyl H-69, Parkmill D, and Perbutyl C, which are commercially available from Nippon Oil & Fats Co., Ltd. , Dialkyl peroxides such as perbutyl D, diacyl peroxides such as Nyper BW, peroxyesters such as perbutyl Z and perbutyl L, peroxydicarbonates such as perroyl TCP, diisobutyryl peroxide, cumylperoxyneodeca Noate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4 -T-Buchi Chlohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methyl Benzoyl) peroxide, t-butylperoxy-2-ethylhexanoe Di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (T-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5, -trimethylhexa Noate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t Butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di (t- Butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di-t-butylperoxyvalerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di -T-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane hydroperoxide, 2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylben Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, 2,4-dichloro Benzoyl peroxide, o-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, tris- (t-butylperoxy) triazine, 2,4,4-trimethylpentylperoxyneodecanoate, α-cumylperoxyneo Decanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxytrimethyladipate, di-3 -Methoxybutyl peroxydicarbonate Di-isopropyl peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, diethylene glycol bis (t-butylperoxycarbonate), t-hexylperoxyneodeca Noate, Lupelox 11 commercially available from Arkema Yoshitosha, etc. are preferably used.
Examples of organic azo compounds include azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70 that are commercially available from Wako Pure Chemical Industries, Ltd., VA-080. Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidines such as V-50 and VA-057 Compounds, azo ester compounds such as V-601, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2- Azobis (2-methylpropionitrile), 2,2-azobis (2,4-dimethylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 1- [ (1-cyano-1-methylethyl) azo] formamide, 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2- Azobis [2-methyl-N- (2-hydroxybutyl) propionamide], 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2-azobis (N-butyl-2) -Methylpropionamide), 2,2-azobis (N-cyclohexyl-2-methylpropioamide), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2- Azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2-azobis {2- [1- (2-hydroxyethyl) -2- Midazolin-2-yl] propane} dihydrochloride, 2,2-azobis [2- [2-imidazolin-2-yl] propane], 2,2-azobis (1-imino-1-pyrrolidino-2-methylpropane) Dihydrochloride, 2,2-azobis (2-methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, dimethyl 2,2-azobis ( 2-methylpropionate), 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2,4,4-trimethylpentane) and the like are preferably used.
重合開始剤の10時間半減期温度は、100℃以下であることが好ましい。10時間半減期温度が100℃以下であれば、重合開始剤を反応終了時に残存しないようにすることが容易である。
重合開始剤は1種のみ、または2種以上を混合して用いてもよい。
重合開始剤の使用量はモノマー1モルに対して、好ましくは0.0001~2モル、より好ましくは0.003~1モル、特に好ましくは0.001~0.5モルである。 The polymerization initiator is preferably an organic azo compound in view of the safety of the reagent itself and the molecular weight reproducibility of the polymerization reaction. Among them, an azo ester compound such as V-601 that does not incorporate harmful cyano into the polymer is preferable.
The 10-hour half-life temperature of the polymerization initiator is preferably 100 ° C. or lower. If the 10-hour half-life temperature is 100 ° C. or less, it is easy to prevent the polymerization initiator from remaining at the end of the reaction.
Only one polymerization initiator or a mixture of two or more polymerization initiators may be used.
The amount of the polymerization initiator used is preferably 0.0001 to 2 mol, more preferably 0.003 to 1 mol, and particularly preferably 0.001 to 0.5 mol with respect to 1 mol of the monomer.
重合反応終了時のポリマーのZ+1平均分子量(MZ+1)は10×104~60×104であることが好ましく、9×104~55×104であることがより好ましく、8×104~40×104であることが最も好ましい。
重合反応終了時の重合体は、分子量300×104以上の成分を実質的に含まないことが好ましく、200×104以上の成分を実質的に含まないことがより好ましく、100×104以上の成分を含まないことが最も好ましい。
重合時に、これらの分子量条件を満たすと、塗布面状がよく、焼成時の膜減りが小さい膜形成用組成物を収率よく製造することができる。 The weight average molecular weight (M w ) of the polymer at the end of the polymerization reaction is preferably 2 × 10 4 to 50 × 10 4 , more preferably 3 × 10 4 to 40 × 10 4. Most preferably, it is 10 4 to 40 × 10 4 .
The Z + 1 average molecular weight (M Z + 1 ) of the polymer at the end of the polymerization reaction is preferably 10 × 10 4 to 60 × 10 4 , more preferably 9 × 10 4 to 55 × 10 4 , and 8 × 10 4. Most preferred is ˜40 × 10 4 .
The polymer at the end of the polymerization reaction is preferably substantially free of components having a molecular weight of 300 × 10 4 or more, more preferably substantially free of components of 200 × 10 4 or more, and 100 × 10 4 or more. It is most preferable not to contain these components.
When these molecular weight conditions are satisfied at the time of polymerization, a film-forming composition having a good coated surface and a small film loss upon firing can be produced with high yield.
例えば、上記重合体が難溶または不溶の溶媒(貧溶媒)を、該反応溶液の10倍以下の体積量、好ましくは10~5倍の体積量で、接触させることにより重合体を固体として析出させる。重合体溶液からの沈殿または再沈殿操作の際に用いる溶媒(沈殿または再沈殿溶媒)としては、該重合体の貧溶媒であればよく、重合体の種類に応じて、炭化水素、ハロゲン化炭化水素、ニトロ化合物、エーテル、ケトン、エステル、カーボネート、アルコール、カルボン酸、水、これらの溶媒を含む混合溶媒等の中から適宜選択して使用できる。これらの中でも、沈殿または再沈殿溶媒として、少なくともアルコール(特に、メタノールなど)または水を含む溶媒が好ましい。 When producing the compound (A), the reaction solution obtained by subjecting the compound (I) to the polymerization reaction may be used as it is, but it is preferable to carry out a purification treatment after completion of the reaction. Purification methods include water-washing and a liquid-liquid extraction method that removes residual monomers and oligomer components by combining with an appropriate solvent, ultrafiltration that extracts only those with a specific molecular weight or less, centrifugation, and column A purification method in a solution state such as chromatography, a reprecipitation method in which the polymer solution is solidified in the poor solvent by dropping the polymer solution into the poor solvent, and the residual weight is removed by filtration. A usual method such as a purification method in a solid state such as washing the combined slurry with a poor solvent can be applied.
For example, the polymer is precipitated as a solid by contacting a solvent in which the polymer is hardly soluble or insoluble (poor solvent) in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution. Let The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon or halogenated carbonization depending on the type of polymer. It can be suitably selected from hydrogen, nitro compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like. Among these, as the precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
沈殿または再沈殿する際の温度としては、効率や操作性を考慮して適宜選択できるが、通常0~50℃程度、好ましくは室温付近(例えば20~35℃程度)である。沈殿または再沈殿操作は、攪拌槽などの慣用の混合容器を用い、バッチ式、連続式等の公知の方法により行うことができる。
沈殿または再沈殿した重合体は、通常、濾過、遠心分離等の慣用の固液分離に付し、乾燥して使用に供される。濾過は、耐溶剤性の濾材を用い、好ましくは加圧下で行われる。乾燥は、常圧または減圧下(好ましくは減圧下)、30~100℃程度、好ましくは30~50℃程度の温度で行われる。 The amount of the precipitation or reprecipitation solvent to be used can be appropriately selected in consideration of efficiency, yield and the like. More preferably, it is 300 to 1000 parts by mass.
The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
良溶媒としては、酢酸エチル、酢酸ブチル、トルエン、メチルエチルケトン、テトラヒドロフランなどが好ましい。良溶媒として、本発明の重合体の等質量~50倍質量を用いることが好ましく、2倍質量~20倍質量用いることがより好ましい。 The polymer may be once precipitated and separated, and then dissolved again in a good solvent, and the polymer may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the polymerization reaction, the polymer is brought into contact with a hardly soluble or insoluble solvent, the polymer is precipitated (step a), the polymer is separated from the solution (step b), and again dissolved in a good solvent to be recycled. A combined solution A is prepared (step c), and then a solvent in which the polymer is hardly soluble or insoluble is added to the polymer solution A in a volume amount less than 10 times that of the polymer solution A (preferably a volume of 5 times or less). The method may include depositing a polymer solid by contacting (step d) and separating the precipitated polymer (step e).
As the good solvent, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone, tetrahydrofuran and the like are preferable. As the good solvent, it is preferable to use an equal mass to 50 times mass of the polymer of the present invention, and it is more preferable to use 2 times mass to 20 times mass.
共役ジエン構造を有する化合物(B)は、上述化合物(A)とディールス・アルダー反応可能な共役ジエン構造を有する化合物である。共役ジエン構造としては、特に限定されず、上述した例示構造などが挙げられる。なお、共役ジエン構造を有する化合物(B)は、1種単独で使用してもよいし、2種以上を併用してもよい。 <Compound (B) having conjugated diene structure>
The compound (B) having a conjugated diene structure is a compound having a conjugated diene structure capable of Diels-Alder reaction with the compound (A). It does not specifically limit as a conjugated diene structure, The example structure mentioned above etc. are mentioned. In addition, the compound (B) which has a conjugated diene structure may be used individually by 1 type, and may use 2 or more types together.
その他に共役ジエン構造を有する化合物としては、共役ジエン構造を有する炭化水素化合物などが挙げられ、より具体的には、1,3-ブタジエン、イソプレン、1,3-ペンタジエン、1,3-ヘキサジエン、1,3-オクタジエン、エチリデンノルボルネン、ビニルノルボルネン、ジシクロペンタジエン、シクロペンタジエン、ペンタメチルシクロペンタジエン、4-エチリデン-8-メチル-1,7-ノナジエン、2,3-ジメチル-1,3-ブタジエン、2-メチル-1,3-ペンタジエン、4,5-ジエチル-1,3-オクタジエン、3-ブチル-1,3-オクタジエン、1,3,7-オクタトリエン、シクロオクタジエン、ノルボルナジエン、1,3,5,5-テトラメチル-1,3-シクロヘキサジエン、α-フェランドレン、α-テルピネン、1,2,3,4-テトラフェニル-1,3-シクロペンタジエン、1,2,3,4,5-ペンタフェニル-1,3-シクロペンタジエン、テトラフェニルシクロペンタジエノン、フラン、チオフェン、ピロール、N-メチルピロール、N-フェニルピロールなどが挙げられる。
これらのなかでは、ジシクロペンタジエン、シクロペンタジエン、ペンタメチルシクロペンタジエン、α-フェランドレン、α-テルピネン、テトラフェニルシクロペンタジエノンが好ましい。 Any compound having a conjugated diene structure can be used as the compound having a conjugated diene structure, and a low molecular weight diene capable of volatilization is preferred. Examples of the compound having a conjugated diene structure are described as diene in Dienes in the Diels-Alder Reaction (Wiley-Interscience, 1990), The Diels-Alder Reaction: Selected Practical Methods (John Wiley & Sons Inc, 2002). And the like.
Other examples of the compound having a conjugated diene structure include hydrocarbon compounds having a conjugated diene structure, and more specifically, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, cyclopentadiene, pentamethylcyclopentadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3,7-octatriene, cyclooctadiene, norbornadiene, 1,3 , 5,5-tetramethyl-1,3-cyclohexadiene, α-ferrandylene, -Terpinene, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene, tetraphenylcyclopentadienone, furan, Examples include thiophene, pyrrole, N-methylpyrrole, N-phenylpyrrole.
Of these, dicyclopentadiene, cyclopentadiene, pentamethylcyclopentadiene, α-ferrandylene, α-terpinene, and tetraphenylcyclopentadienone are preferable.
一般式(B-1)および一般式(B-2)中、Wは、-O-、-C(O)-、-C(O)O-、-S(O)-、-S(O)2-、-C(X17)(X18)-、または、-N(X19)-を表す。X17~X19は、それぞれ独立に、水素原子または置換基を表す。 In the general formulas (B-1) to (B-3), X 1 to X 16 each independently represents a hydrogen atom or a substituent.
In the general formulas (B-1) and (B-2), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (X 17 ) (X 18 ) —, or —N (X 19 ) —. X 17 to X 19 each independently represents a hydrogen atom or a substituent.
また、X17~X19は、それぞれ独立に、水素原子または置換基を表す。X17~X19で表される置換基は、上記のX1~X16で表される置換基と同義である。 In general formula (B-1), X 1 to X 16 each independently represents a hydrogen atom or a substituent. The substituents represented by X 1 to X 16 have the same meanings as the substituents represented by Y 1 to Y 11 in formulas (F-1) to (F-4). Of these, an alkyl group, a cycloalkyl group, an aryl group, a silicon atom-containing group and the like are preferable.
X 17 to X 19 each independently represent a hydrogen atom or a substituent. The substituents represented by X 17 to X 19 have the same meanings as the substituents represented by X 1 to X 16 above.
ジエン構造を有する化合物の付加量(含有量)は、化合物(Y)全量に対して、5~80質量%が好ましく、5~60質量%がより好ましく、10~50質量%がさらに好ましい。上記範囲であれば、連結孔の生成が抑えられ、また膜平坦性の点で好ましい。ジエン構造を有する化合物の付加量はNMRスペクトルや、加熱または冷却しながら質量変化を測定する熱重量分析 (TGA)、比熱や反応熱の変化を測定する示差熱分析(DTA)や示差走査熱量測定(DSC)によって定量できる。 In a coating film containing the compound (Y) obtained by bonding the compound (B) having such a diene structure to the compound (A) having a siloxane structure, heating, light irradiation, radiation irradiation, or a combination thereof is performed. The reverse Diels-Alder reaction can be advanced by carrying out the hardening process used. As a result, the compound (B) having a diene structure that acts as a pore-forming agent volatilizes from the compound (Y) to increase the film gap and further causes a curing reaction between the residues, resulting in a low dielectric constant and a high refractive index. Film having a high dielectric constant, a high mechanical strength, a high heat resistance, and a high resistance to oxidative stress and having a long-term dielectric constant.
The addition amount (content) of the compound having a diene structure is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass with respect to the total amount of the compound (Y). If it is the said range, the production | generation of a connection hole will be suppressed and it is preferable at the point of film | membrane flatness. Addition amount of compound having diene structure is NMR spectrum, thermogravimetric analysis (TGA) to measure mass change while heating or cooling, differential thermal analysis (DTA) to measure change of specific heat and reaction heat, differential scanning calorimetry Can be quantified by (DSC).
なお、本発明では化合物(Y)を使用すると、比較的気体透過性のよいシロキサン構造の膜が得られるため、化合物(B)の揮発がより容易となり所望のサイズの空孔が形成されたと推測される。 In the present invention, when the compound (Y) synthesized using the compound (B) is used, the compound (B) that acts as a pore-forming agent at the time of hardening is released, and at the same time, a dienophile structure that can be a cross-linked portion is generated. The Therefore, pore formation and membrane crosslinking can proceed simultaneously in the same region in the film, and a large number of pores having smaller sizes and uniform sizes can be formed uniformly in the film. When using a known pore-forming agent, the pore-forming agents usually aggregate to form a large domain, and the region where the pore-forming agent volatilizes and the region where the cross-linked structure is formed are separated. As a result, a film having only large pores and a non-uniform size distribution and having insufficient mechanical strength is produced.
In the present invention, when a compound (Y) is used, a film having a relatively good gas permeability and a siloxane structure can be obtained. Therefore, it is presumed that the volatilization of the compound (B) becomes easier and pores of a desired size are formed. Is done.
上記化合物(A)と化合物(B)とをディールス・アルダー反応を行う条件は、使用する化合物の種類などにより適宜最適な条件が選択される。
ディールス・アルダー反応を行う反応溶媒としては、使用する化合物が溶解し、反応に影響を与えない溶媒であれば特に限定されない。例えば、上記の化合物(I)の重合反応に使用される溶媒などが挙げられる。
反応温度は、特に制限されないが、通常25℃~250℃であり、好ましくは50℃~200℃、さらに好ましくは80℃~200℃である。 <Reaction conditions>
The conditions under which the Diels-Alder reaction is performed between the compound (A) and the compound (B) are appropriately selected depending on the type of compound used.
The reaction solvent for performing the Diels-Alder reaction is not particularly limited as long as the compound to be used dissolves and does not affect the reaction. For example, the solvent etc. which are used for the polymerization reaction of said compound (I) are mentioned.
The reaction temperature is not particularly limited, but is usually 25 ° C to 250 ° C, preferably 50 ° C to 200 ° C, more preferably 80 ° C to 200 ° C.
また、酸素による重合開始剤の不活性化を抑制するために、不活性ガス雰囲気下(例えば、窒素、アルゴン等)で反応させることが好ましい。反応時の酸素濃度は、好ましくは100ppm以下、より好ましくは50ppm以下、特に好ましくは20ppm以下である。
反応終了後、上記化合物(A)で述べた精製処理を実施することが好ましい。
化合物(Y)の製造工程においては、重合反応を抑制するために重合禁止剤を添加することが好ましい。重合禁止剤の例としては、4-メトキシフェノール、2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール、カテコールなどが挙げられる。なかでも、4-メトキシフェノール、2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノールが特に好ましい。重合禁止剤の添加量は、シロキサン構造を有する化合物(A)全量に対して、5質量%以上が好ましい。 The concentration of the compound (A) in the reaction solution is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total amount of the reaction solution. By setting the concentration range, the generation of impurities such as gelling components can be suppressed.
Moreover, in order to suppress inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
After completion of the reaction, it is preferable to carry out the purification treatment described in the compound (A).
In the production process of compound (Y), it is preferable to add a polymerization inhibitor in order to suppress the polymerization reaction. Examples of the polymerization inhibitor include 4-methoxyphenol, 2,6-bis (1,1-dimethylethyl) -4-methylphenol, catechol and the like. Of these, 4-methoxyphenol and 2,6-bis (1,1-dimethylethyl) -4-methylphenol are particularly preferable. The addition amount of the polymerization inhibitor is preferably 5% by mass or more based on the total amount of the compound (A) having a siloxane structure.
本発明の組成物には、上記の化合物(X)が含有される。なお、本発明の組成物は、化合物(X)が溶剤(例えば、有機溶剤)に溶解した溶液であってもよいし、化合物(X)の反応物を含む固形物であってもよい。
本発明の組成物は、種々の用途に用いることができ、その目的に応じて化合物(X)の含有量や添加する添加剤などの種類が決められる。用途としては、例えば、膜(例えば、絶縁膜)を製造するため(膜形成用組成物)や、低屈折率膜、低屈折率材料、ガス吸着材料、レジスト材料などが挙げられる。 <Composition>
The composition of the present invention contains the above compound (X). The composition of the present invention may be a solution in which the compound (X) is dissolved in a solvent (for example, an organic solvent), or may be a solid containing a reaction product of the compound (X).
The composition of the present invention can be used in various applications, and the type of the content of the compound (X) and the additive to be added is determined according to the purpose. Applications include, for example, for producing a film (for example, an insulating film) (film forming composition), a low refractive index film, a low refractive index material, a gas adsorbing material, a resist material, and the like.
溶剤としては、25℃で化合物(X)を5質量%以上溶解する溶剤が好ましく、10質量%以上がより好ましい。具体的には、エチレンジクロライド、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、メチルイソブチルケトン、γ-ブチロラクトン、メチルエチルケトン、メタノール、エタノール、ジメチルイミダゾリジノン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、2-メトキシエチルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、テトラエチレングリコールジメチルエーテル、トリエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、イソプロパノール、エチレンカーボネート、酢酸エチル、酢酸ブチル、乳酸メチル、乳酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、N,N-ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、N-メチルピロリドン、テトラヒドロフラン、ジイソプロピルベンゼン、トルエン、キシレン、メシチレン等が好ましく、これらの溶剤を単独あるいは混合して使用する。
上記の中でも、好ましい溶剤としてはプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、2-ヘプタノン、シクロヘキサノン、γ-ブチロラクトン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、エチレンカーボネート、酢酸ブチル、乳酸メチル、乳酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、N-メチルピロリドン、N,N-ジメチルホルムアミド、テトラヒドロフラン、メチルイソブチルケトン、キシレン、メシチレン、ジイソプロピルベンゼンを挙げることができる。 The composition of the present invention may contain a solvent. That is, it is preferable to use the compound (X) by dissolving it in an appropriate solvent and coating it on a support.
As a solvent, the solvent which melt | dissolves 5 mass% or more of compound (X) at 25 degreeC is preferable, and 10 mass% or more is more preferable. Specifically, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, methyl isobutyl ketone, γ-butyrolactone, methyl ethyl ketone, methanol, ethanol, dimethylimidazolidinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Dimethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetraethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, isopropanol , Ethylene carbon , Ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N -Methylpyrrolidone, tetrahydrofuran, diisopropylbenzene, toluene, xylene, mesitylene and the like are preferable, and these solvents are used alone or in combination.
Among these, preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, Mention may be made of mesitylene and diisopropylbenzene.
組成物中の金属濃度は、組成物を用いて得られた膜に対して全反射蛍光X線測定を行うことによっても評価できる。X線源としてW線を用いた場合、金属元素としてK、Ca、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Pdが観測可能であり、それぞれ100×1010cm-2以下が好ましく、より好ましくは50×1010cm-2以下、特に好ましくは10×1010cm-2以下である。また、ハロゲンであるBrも観測可能であり、残存量は10000×1010cm-2以下が好ましく、より好ましくは1000×1010cm-2以下、特に好ましくは400×1010cm-2以下である。また、ハロゲンとしてClも観測可能であるが、CVD装置、エッチング装置等へダメージを与えるという観点から残存量は100×1010cm-2以下が好ましく、より好ましくは50×1010cm-2以下、特に好ましくは10×1010cm-2以下である。 In the composition of the present invention, the metal content as an impurity is preferably sufficiently small. The metal concentration in the composition can be measured with high sensitivity by the ICP-MS method or the like, and the metal content other than the transition metal in that case is preferably 30 ppm or less, more preferably 3 ppm or less, and particularly preferably 300 ppb or less. . In addition, the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the pre-baking and thermosetting processes described later, the content is lower. It is preferably 10 ppm or less, more preferably 1 ppm or less, particularly preferably 100 ppb or less.
The metal concentration in the composition can also be evaluated by performing total reflection X-ray fluorescence measurement on the film obtained using the composition. When W line is used as the X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, and each is 100 × 10 10 cm −2 or less. Is more preferably 50 × 10 10 cm −2 or less, and particularly preferably 10 × 10 10 cm −2 or less. Further, Br which is halogen can be observed, and the residual amount is preferably 10000 × 10 10 cm −2 or less, more preferably 1000 × 10 10 cm −2 or less, particularly preferably 400 × 10 10 cm −2 or less. is there. Further, although Cl can be observed as halogen, the remaining amount is preferably 100 × 10 10 cm −2 or less, more preferably 50 × 10 10 cm −2 or less from the viewpoint of damaging a CVD apparatus, an etching apparatus, or the like. Particularly preferably, it is 10 × 10 10 cm −2 or less.
更に、本発明の組成物には、組成物を用いて得られる膜の特性(耐熱性、誘電率、機械強度、塗布性、密着性等)を損なわない範囲で、ラジカル発生剤、コロイド状シリカ、界面活性剤、密着剤などの添加剤を添加してもよい。 <Additives>
Furthermore, the composition of the present invention includes a radical generator and colloidal silica as long as the properties (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) of the film obtained using the composition are not impaired. Additives such as surfactants and adhesives may be added.
密着促進剤の好ましい使用量は、特に制限されないが、通常、組成物中の全固形分に対して、10質量%以下、特に0.05~5質量%であることが好ましい。 Any adhesion promoter may be used in the composition of the present invention as long as the object of the present invention is not impaired. For example, 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-amino Propyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4 7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl- 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxy Silane, trimethoxysilyl repose Acid, 3-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane aluminum monoethyl acetoacetate diisopropylate, vinyltris (2-methoxyethoxy) silane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Xysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, dimethylvinylethoxysilane, diphenyl Dimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole , 2-mercaptobenzothiazole, 2-mercaptobenzoxa Lumpur, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, may be mentioned thiourea compounds. Functional silane coupling agents are preferred as adhesion promoters. Only one type of adhesion promoter used in the present invention may be used, or two or more types may be used in combination.
The preferred use amount of the adhesion promoter is not particularly limited, but it is usually preferably 10% by mass or less, particularly preferably 0.05 to 5% by mass with respect to the total solid content in the composition.
本発明の組成物は、上記のように種々の用途に用いることができる。例えば、その用途としては、絶縁膜を作製するために使用することができる(以下、適宜、膜形成用組成物と称する。)。
本発明の膜形成用組成物を使用して得られる絶縁膜は、膜形成用組成物をスピンコーティング法、ローラーコーティング法、ディップコーティング法、スキャン法、スプレー法、バー塗布法等の任意の方法により、シリコンウエハ、SiO2ウエハ、SiNウエハ、ガラス、プラスチックフィルムなどの基板に塗布した後、溶剤を必要に応じて加熱処理で除去することにより形成することができる。
基板に塗布する方法としては、スピンコーティング法、スキャン法によるものが好ましい。特に好ましくは、スピンコーティング法によるものである。スピンコーティングについては、市販の装置を使用できる。例えば、クリーントラックシリーズ(東京エレクトロン製)、D-スピンシリーズ(大日本スクリーン製)、SSシリーズあるいはCSシリーズ(東京応化工業製)等が好ましく使用できる。
スピンコート条件としては、いずれの回転速度でもよいが、絶縁膜の面内均一性の観点より、300mmシリコン基板においては1300rpm程度の回転速度が好ましい。また組成物溶液の吐出方法においては、回転する基板上に組成物溶液を吐出する動的吐出、静止した基板上へ組成物溶液を吐出する静的吐出のいずれでもよいが、膜の面内均一性の観点より、動的吐出が好ましい。また、組成物の消費量を抑制する観点より、予備的に組成物の主溶剤のみを基板上に吐出して液膜を形成した後、その上から組成物を吐出するという方法を用いることもできる。スピンコート時間については特に制限はないが、スループットの観点から180秒以内が好ましい。また、基板の搬送の観点より、基板エッジ部の膜を残存させないための処理(エッジリンス、バックリンス)をすることも好ましい。
熱処理の方法は、特に限定されないが、一般的に使用されているホットプレート加熱、ファーネス炉を使用した加熱方法、RTP(Rapid Thermal Processor)等によるキセノンランプを使用した光照射加熱等を適用することができる。好ましくは、ホットプレート加熱、ファーネスを使用した加熱方法である。ホットプレートとしては市販の装置を好ましく使用でき、クリーントラックシリーズ(東京エレクトロン製)、D-スピンシリーズ(大日本スクリーン製)、SSシリーズあるいはCSシリーズ(東京応化工業製)等が好ましく使用できる。ファーネスとしては、αシリーズ(東京エレクトロン製)等が好ましく使用できる。 <Membrane manufacturing method>
The composition of the present invention can be used for various applications as described above. For example, it can be used for producing an insulating film (hereinafter referred to as a film-forming composition as appropriate).
The insulating film obtained by using the film forming composition of the present invention can be obtained by any method such as spin coating method, roller coating method, dip coating method, scanning method, spray method, bar coating method, etc. Thus, after applying to a substrate such as a silicon wafer, a SiO 2 wafer, a SiN wafer, glass, or a plastic film, the solvent can be removed by heat treatment as necessary.
As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, the clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used.
The spin coating conditions may be any rotational speed, but a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate from the viewpoint of in-plane uniformity of the insulating film. In addition, the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.
The method of heat treatment is not particularly limited, but it is possible to apply commonly used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. Can do. A heating method using hot plate heating or furnace is preferable. A commercially available apparatus can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron), D-Spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.
高エネルギー線として、電子線を使用した場合のエネルギーは0.1~50keVが好ましく、より好ましくは0.2~30keV、特に好ましくは0.5~20keVである。電子線の総ドーズ量は好ましくは0.01~5μC/cm2、より好ましくは0.01~2μC/cm2、特に好ましくは0.01~1μC/cm2である。電子線を照射する際の基板温度は0~500℃が好ましく、より好ましくは20~450℃、特に好ましくは20~400℃である。圧力は好ましくは0~133kPa、より好ましくは0~60kPa、特に好ましくは0~20kPaである。
本発明の重合物の酸化を防止するという観点から、基板周囲の雰囲気はAr、He、窒素などの不活性雰囲気を用いることが好ましい。また、電子線との相互作用で発生するプラズマ、電磁波、化学種との反応を目的に酸素、炭化水素、アンモニアなどのガスを添加してもよい。電子線照射は複数回行ってもよく、この場合は電子線照射条件を毎回同じにする必要はなく、毎回異なる条件で行ってもよい。 Further, in the present invention, the film may be hardened by causing a polymerization reaction of a vinyl group or an ethynyl group remaining in the compound (X) by irradiating with high energy rays such as light irradiation and radiation irradiation instead of heat treatment. Good. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 0.1 to 50 keV, more preferably 0.2 to 30 keV, and particularly preferably 0.5 to 20 keV. The total dose of the electron beam is preferably 0.01 to 5 μC / cm 2 , more preferably 0.01 to 2 μC / cm 2 , and particularly preferably 0.01 to 1 μC / cm 2 . The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 500 ° C., more preferably 20 to 450 ° C., and particularly preferably 20 to 400 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa.
From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.
カゴ構造が焼成時に分解しないために、組成物および膜の製造中にSi原子に求核攻撃する基(水酸基、シラノール基など)が実質的に存在しないことが好ましい。 The film thickness when forming the insulating film is a dry film thickness of about 0.05 to 1.5 μm with a single coating, and a coating with a thickness of about 0.1 to 3 μm with a second coating. Can do.
Since the cage structure does not decompose during firing, it is preferable that groups (hydroxyl groups, silanol groups, etc.) that nucleophilically attack Si atoms are not substantially present during the production of the composition and film.
上述した膜形成用組成物から得られる絶縁膜の厚さは、特に限定されないが、0.005~10μmであることが好ましく、0.01~5.0μmであることがより好ましく、0.01~1.0μmであることがさらに好ましい。
ここで、本発明の絶縁膜の厚さは、光学干渉式膜厚測定器にて任意の3箇所以上を測定した場合の単純平均値を意味するものとする。 <Insulating film>
The thickness of the insulating film obtained from the film forming composition described above is not particularly limited, but is preferably 0.005 to 10 μm, more preferably 0.01 to 5.0 μm, More preferably, it is -1.0 μm.
Here, the thickness of the insulating film of the present invention means a simple average value when three or more arbitrary positions are measured with an optical interference type film thickness measuring instrument.
最大分布直径は、3nm以下がより好ましい。なお、最大分布直径の下限は、特に制限されないが、公知の測定装置により測定可能な下限として0.5nmが挙げられる。
なお、最大分布直径とは、窒素ガス吸着法により得られた空孔分布曲線における最大ピークを示す空孔直径を意味する。 The film obtained from the film-forming composition described above is preferably a porous film, and the pore diameter (hereinafter also referred to as the maximum distribution diameter) indicating the maximum peak in the pore distribution curve of the pores in the porous film is It is preferable that it is 5 nm or less. When the maximum distribution diameter is 5 nm or less, it is possible to achieve both excellent mechanical strength and relative dielectric constant characteristics.
The maximum distribution diameter is more preferably 3 nm or less. The lower limit of the maximum distribution diameter is not particularly limited, but a lower limit that can be measured by a known measuring apparatus is 0.5 nm.
The maximum distribution diameter means a hole diameter showing a maximum peak in a hole distribution curve obtained by a nitrogen gas adsorption method.
本発明の絶縁膜は、多様の目的に使用することができ、特に電子デバイスへ好適に用いることができる。電子デバイスとは、半導体装置や、磁気記録ヘッドなどを含めた広範な電子機器を意味する。例えば、LSI、システムLSI、DRAM、SDRAM、RDRAM、D-RDRAM等の半導体装置、マルチチップモジュール多層配線板等の電子部品における絶縁皮膜として好適であり、半導体用層間絶縁膜、エッチングストッパー膜、表面保護膜、バッファーコート膜の他、LSIにおけるパッシベーション膜、α線遮断膜、フレキソ印刷版のカバーレイフィルム、オーバーコート膜、フレキシブル銅張板のカバーコート、ソルダーレジスト膜、液晶配向膜等として使用することができる。また、光学装置用の表面保護膜、反射防止膜、位相差膜としても用いることができる。 <Application>
The insulating film of the present invention can be used for various purposes, and can be particularly suitably used for electronic devices. An electronic device means a wide range of electronic equipment including a semiconductor device and a magnetic recording head. For example, it is suitable as an insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, semiconductor interlayer insulating film, etching stopper film, surface In addition to protective films and buffer coat films, it is used as LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper clad cover coats, solder resist films, liquid crystal alignment films, etc. be able to. It can also be used as a surface protective film, an antireflection film, or a retardation film for optical devices.
電子グレード濃塩酸67g、n-ブタノール305g、イオン交換水133gの混合溶液を10℃に冷却し、これにビニルトリエトキシシラン59gを15分間かけて滴下した。その後更に、25℃で18時間攪拌した。析出した結晶を濾取し、電子グレードメタノール50gで洗浄した。これをテトラヒドロフラン42gに溶解し、攪拌しながら電子グレードメタノール42g、続いてイオン交換水127gを滴下した。析出した結晶を濾取、乾燥して白色固体の目的物(化合物I-m)4.2gを得た。1H-NMR測定の結果は以下の通りであった。1H-NMR (300 MHz, CDCl3) :6.13-5.88 (m, 24H) <Synthesis of Compound Im>
A mixed solution of 67 g of electronic grade concentrated hydrochloric acid, 305 g of n-butanol and 133 g of ion-exchanged water was cooled to 10 ° C., and 59 g of vinyltriethoxysilane was added dropwise thereto over 15 minutes. Thereafter, the mixture was further stirred at 25 ° C. for 18 hours. The precipitated crystals were collected by filtration and washed with 50 g of electronic grade methanol. This was dissolved in 42 g of tetrahydrofuran, and 42 g of electronic grade methanol and then 127 g of ion-exchanged water were added dropwise with stirring. The precipitated crystals were collected by filtration and dried to obtain 4.2 g of the desired product (Compound Im) as a white solid. The results of 1 H-NMR measurement were as follows. 1 H-NMR (300 MHz, CDCl3): 6.13-5.88 (m, 24H)
電子グレード濃塩酸136g、n-ブタノール1L、イオン交換水395gの混合溶液を10℃に冷却し、これにビニルトリエトキシシラン78.3gとメチルトリエトキシシラン73.3gの混合溶液を15分間かけて滴下した。その後更に、25℃で18時間攪拌した。析出した結晶を濾取し、電子グレードメタノール100mLで洗浄した。これをテトラヒドロフラン500mLに溶解し、攪拌しながら電子グレードメタノール200mL、続いてイオン交換水200mLを滴下した。析出した結晶を濾取、乾燥して白色固体の目的物(化合物I-k)7.8gを得た。1H-NMR測定の結果は以下の通りであった。1H-NMR (300 MHz, CDCl3) :0.28-0.18 (m, 12H), 6.08-5.88 (m, 12H) <Synthesis of Compound Ik>
A mixed solution of 136 g of electronic grade concentrated hydrochloric acid, 1 L of n-butanol and 395 g of ion-exchanged water was cooled to 10 ° C., and a mixed solution of 78.3 g of vinyltriethoxysilane and 73.3 g of methyltriethoxysilane was added to this over 15 minutes. It was dripped. Thereafter, the mixture was further stirred at 25 ° C. for 18 hours. The precipitated crystals were collected by filtration and washed with 100 mL of electronic grade methanol. This was dissolved in 500 mL of tetrahydrofuran, and 200 mL of electronic grade methanol and then 200 mL of ion-exchanged water were added dropwise with stirring. The precipitated crystals were collected by filtration and dried to obtain 7.8 g of the desired product (Compound Ik) as a white solid. The results of 1 H-NMR measurement were as follows. 1 H-NMR (300 MHz, CDCl3): 0.28-0.18 (m, 12H), 6.08-5.88 (m, 12H)
化合物(I-m)50gを電子グレード酢酸ブチル1320gに加えた。得られた溶液を窒素気流中120℃に加熱し、重合開始剤として和光純薬工業社製V-601(10時間半減温度66℃)0.47gと2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール113mgとを電子グレード酢酸ブチル235mlに溶解させた溶液50.4mlを80分かけて滴下した。滴下終了後、更に1時間120℃にて攪拌した。攪拌終了後、反応液に電子グレードメタノール3L、イオン交換水3Lを加え、析出した固体を濾取し、電子グレードメタノール100mLで洗浄した。これをテトラヒドロフラン724gに溶解し、攪拌しながら電子グレードメタノール50g、続いて水150gを滴下した。1時間攪拌した後、デカンテーションで上澄みを捨て、電子グレードメタノール200gを加えた。析出した固体を濾取、乾燥して白色固体の目的物(樹脂A-1)17.7gを得た。得られた樹脂をGPCで分析すると、Mw=8.7×104、Mn=5.4×104であった。固形物中には未反応の化合物(I-m)は2質量%以下であり、分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基のプロトンピーク(4.9~6.8ppm)が2.6/5.4の積分比率で観察された。 <Synthesis of Resin A-1>
50 g of compound (Im) was added to 1320 g of electronic grade butyl acetate. The obtained solution was heated to 120 ° C. in a nitrogen stream, and 0.47 g of V-601 (10-hour half temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. and 2,6-bis (1,1-dimethyl) were used as polymerization initiators. 50.4 ml of a solution prepared by dissolving 113 mg of ethyl) -4-methylphenol in 235 ml of electronic grade butyl acetate was added dropwise over 80 minutes. After completion of dropping, the mixture was further stirred at 120 ° C. for 1 hour. After completion of the stirring, 3 L of electronic grade methanol and 3 L of ion exchange water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 100 mL of electronic grade methanol. This was dissolved in 724 g of tetrahydrofuran, and 50 g of electronic grade methanol and then 150 g of water were added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 200 g of electronic grade methanol was added. The precipitated solid was collected by filtration and dried to obtain 17.7 g of the desired product (resin A-1) as a white solid. When the obtained resin was analyzed by GPC, M w = 8.7 × 10 4 and M n = 5.4 × 10 4 . In the solid, the unreacted compound (Im) was 2% by mass or less, and no component having a molecular weight of 3 million or more was observed. When 1 H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, a proton peak derived from an alkyl group formed by polymerization of a vinyl group (0.2 to 3.0 ppm) and a proton peak of a remaining vinyl group ( 4.9-6.8 ppm) was observed at an integration ratio of 2.6 / 5.4.
化合物(I-m)109gをジフェニルエーテル2878gに加えた。得られた溶液を窒素気流中120℃に加熱し、重合開始剤として和光純薬工業社製V-601(10時間半減温度66℃)168mgをジフェニルエーテル74gに溶解させた溶液15.0mlを30分かけて滴下した。滴下終了後、更に1時間120℃にて攪拌した。攪拌終了後に、反応液に電子グレードメタノール5.4L、水200mLを加え、析出した固体を濾取し、電子グレードメタノール200mLで洗浄した。これをテトラヒドロフラン1Lに溶解し、攪拌しながら電子グレードメタノール2L、続いてイオン交換水125gを加え、析出した固体を濾取し、電子グレードメタノール200mLで洗浄した。この操作を計2回繰り返し、乾燥して白色固体の目的物(樹脂A-2)7.26gを得た。得られた樹脂をGPCで分析すると、Mw=8.1×104、Mn=4.98×104であった。固形物中には未反応の化合物(I-m)は0.2質量%以下であり、分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基のプロトンピーク(4.9~6.8ppm)が2.2/5.8の積分比率で観察された。 <Synthesis of Resin A-2>
109 g of compound (Im) was added to 2878 g of diphenyl ether. The obtained solution was heated to 120 ° C. in a nitrogen stream, and 15.0 ml of a solution obtained by dissolving 168 mg of V-601 (10-hour half-temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. in 74 g of diphenyl ether as a polymerization initiator for 30 minutes. It was dripped over. After completion of dropping, the mixture was further stirred at 120 ° C. for 1 hour. After completion of the stirring, 5.4 L of electronic grade methanol and 200 mL of water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 200 mL of electronic grade methanol. This was dissolved in 1 L of tetrahydrofuran, 2 L of electronic grade methanol and then 125 g of ion-exchanged water were added with stirring, and the precipitated solid was collected by filtration and washed with 200 mL of electronic grade methanol. This operation was repeated twice in total and dried to obtain 7.26 g of the desired product (resin A-2) as a white solid. When the obtained resin was analyzed by GPC, M w = 8.1 × 10 4 and M n = 4.98 × 10 4 . In the solid, the unreacted compound (Im) was 0.2% by mass or less, and no component having a molecular weight of 3 million or more was observed. When 1 H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, a proton peak derived from an alkyl group formed by polymerization of a vinyl group (0.2 to 3.0 ppm) and a proton peak of a remaining vinyl group ( 4.9-6.8 ppm) was observed at an integration ratio of 2.2 / 5.8.
化合物(I-m)30gをジフェニルエーテル792gに加えた。得られた溶液を窒素気流中150℃に加熱し、重合開始剤として和光純薬工業社製VR-110(Azodi-tert-octane、10時間半減温度110℃)112mgと2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール22mgをジフェニルエーテル49.8gに溶解させた溶液11.4mlを30分かけて滴下した。滴下終了後、更に1時間150℃にて攪拌した。攪拌終了後、反応液に電子グレードメタノール3.5L、イオン交換水150mLを加え、析出した固体を濾取し、電子グレードメタノール200mLで洗浄した。これをテトラヒドロフラン300mLに溶解し、攪拌しながら電子グレードメタノール30mL、続いてイオン交換水60mLを加え、析出した固体を濾取し、電子グレードメタノール100mLで洗浄した。この操作を計2回繰り返し、乾燥して白色固体の目的物(樹脂A-3)12.5gを得た。得られた樹脂をGPCで分析すると、Mw=18.3×104、Mn=5.58×104であった。固形物中には未反応の化合物(I-m)は2質量%以下であり、分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基のプロトンピーク(4.9~6.8ppm)が1.3/6.7の積分比率で観察された。 <Synthesis of Resin A-3>
30 g of compound (Im) was added to 792 g of diphenyl ether. The resulting solution was heated to 150 ° C. in a nitrogen stream, and 112 mg of VR-110 (Azodi-tert-octane, 10 hour half-temperature 110 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. as a polymerization initiator and 2,6-bis (1 , 1-dimethylethyl) -4-methylphenol 22 ml of a solution of 49.8 g of diphenyl ether dissolved therein was added dropwise over 30 minutes. After completion of dropping, the mixture was further stirred at 150 ° C. for 1 hour. After completion of the stirring, 3.5 L of electronic grade methanol and 150 mL of ion-exchanged water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 200 mL of electronic grade methanol. This was dissolved in 300 mL of tetrahydrofuran, 30 mL of electronic grade methanol and then 60 mL of ion-exchanged water were added with stirring, and the precipitated solid was collected by filtration and washed with 100 mL of electronic grade methanol. This operation was repeated twice in total and dried to obtain 12.5 g of the desired product (resin A-3) as a white solid. When the obtained resin was analyzed by GPC, it was Mw = 18.3 × 10 4 and M n = 5.58 × 10 4 . In the solid, the unreacted compound (Im) was 2% by mass or less, and no component having a molecular weight of 3 million or more was observed. When 1 H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, a proton peak derived from an alkyl group formed by polymerization of a vinyl group (0.2 to 3.0 ppm) and a proton peak of a remaining vinyl group ( (4.9 to 6.8 ppm) was observed at an integration ratio of 1.3 / 6.7.
化合物(I-m)1gを電子グレード酢酸ブチル26.4gに加えた。得られた溶液を窒素気流中、内温127℃で加熱還流しながら、重合開始剤として和光純薬工業製V-601(10時間半減温度66℃)1.8mgを電子グレード酢酸ブチル2mlに溶解させた溶液を2時間かけて滴下した。滴下終了後、さらに1時間加熱還流した。重合禁止剤として4-メトキシフェノール20mgを加えた後、室温まで冷却した。その後、液重量2gまで減圧濃縮し、電子グレードメタノール20mlを加え、1時間攪拌した後、固形物を濾取、乾燥した。これをテトラヒドロフラン15mlに溶解し、攪拌しながらイオン交換水5mlを滴下した。1時間攪拌した後、デカンテーションで上澄みを捨て、電子グレードメタノール10mlを加えた。固形分を濾取、乾燥し、白色固体の目的物(樹脂A-4)0.60gを得た。得られた樹脂をGPCで分析すると、Mw=11.8×104、Mn=3.1×104、Mz+1=27×104であった。固形物中には未反応の化合物(I-m)は3質量%以下であり、分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、固形分の1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基のプロトンピーク(4.9~6.8ppm)が42/58の積分比率で観察された。 <Synthesis of Resin A-4>
1 g of compound (Im) was added to 26.4 g of electronic grade butyl acetate. While heating and refluxing the resulting solution at an internal temperature of 127 ° C. in a nitrogen stream, 1.8 mg of Wako Pure Chemical Industries V-601 (10-hour half-temperature 66 ° C.) as a polymerization initiator was dissolved in 2 ml of electronic grade butyl acetate. The solution was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further heated to reflux for 1 hour. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature. Thereafter, the solution was concentrated under reduced pressure to a liquid weight of 2 g, 20 ml of electronic grade methanol was added and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 15 ml of tetrahydrofuran, and 5 ml of ion-exchanged water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation and 10 ml of electronic grade methanol was added. The solid content was collected by filtration and dried to obtain 0.60 g of the desired product (resin A-4) as a white solid. When the obtained resin was analyzed by GPC, it was Mw = 11.8 × 10 4 , Mn = 3.1 × 10 4 , and M z + 1 = 27 × 10 4 . In the solid, the unreacted compound (Im) was 3% by mass or less, and no component having a molecular weight of 3 million or more was observed. When 1 H-NMR spectrum of a solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group-derived proton peak (0.2 to 3.0 ppm) generated by polymerization of the vinyl group and the remaining vinyl group A proton peak (4.9-6.8 ppm) was observed with an integral ratio of 42/58.
化合物(I-m)1gを電子グレード酢酸ブチル13.2gに加えた。得られた溶液を窒素気流中、内温127℃で加熱還流しながら、重合開始剤として和光純薬工業製V-40(10時間半減温度88℃)1mgを電子グレード酢酸ブチル1mlに溶解させた溶液を4時間かけて滴下した。滴下終了後、1時間加熱還流した。重合禁止剤として4-メトキシフェノール20mgを加えた後、室温まで冷却した。その後、液重量2gまで減圧濃縮し、電子グレードメタノール20mlを加え、1時間攪拌した後、固形物をろ取、乾燥した。これをテトラヒドロフラン10mlに溶解し、攪拌しながらイオン交換水1.8mlを滴下した。1時間攪拌した後、デカンテーションで上澄みを捨て、電子グレードメタノール10mlを加えた。固形分を濾取、乾燥し、白色固体の目的物(樹脂A-5)0.41gを得た。得られた樹脂をGPCで分析すると、Mw=12.8×104、Mn=3.3×104、Mz+1=38×104であった。固形物中には未反応の例示化合物(I-m)は3質量%以下であり、分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、固形分の1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基のプロトンピーク(4.9~6.8ppm)が53:47の積分比率で観察された。 <Synthesis of Resin A-5>
1 g of compound (Im) was added to 13.2 g of electronic grade butyl acetate. While heating and refluxing the obtained solution at an internal temperature of 127 ° C. in a nitrogen stream, 1 mg of W-40 (manufactured by Wako Pure Chemical Industries, Ltd.) V-40 (10 hours half-temperature 88 ° C.) was dissolved in 1 ml of electronic grade butyl acetate. The solution was added dropwise over 4 hours. After completion of dropping, the mixture was heated to reflux for 1 hour. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature. Thereafter, the solution was concentrated under reduced pressure to a liquid weight of 2 g, 20 ml of electronic grade methanol was added and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 10 ml of tetrahydrofuran, and 1.8 ml of ion-exchanged water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation and 10 ml of electronic grade methanol was added. The solid content was collected by filtration and dried to obtain 0.41 g of the desired product (resin A-5) as a white solid. When the obtained resin was analyzed by GPC, M w = 12.8 × 10 4 , M n = 3.3 × 10 4 , and M z + 1 = 38 × 10 4 . In the solid, the unreacted exemplary compound (Im) was 3% by mass or less, and no component having a molecular weight of 3 million or more was observed. When 1 H-NMR spectrum of a solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group-derived proton peak (0.2 to 3.0 ppm) generated by polymerization of the vinyl group and the remaining vinyl group A proton peak (4.9-6.8 ppm) was observed at an integration ratio of 53:47.
樹脂(A-1)800mg、2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール50mg、ジシクロペンタジエン8gをジフェニルエーテル4gに加えた。
得られた溶液を窒素気流中180℃に加熱し、3時間攪拌した。攪拌終了後、反応液を電子グレードメタノール200mlに加え、析出固体を濾取、乾燥し、一般式(F-2)で表されるディールス・アルダー反応付加部を有する白色固体の目的物(樹脂X-1)820mgを得た。得られた樹脂をGPCで分析すると、Mw=11.5×104、Mn=5.29×104であった。固形物中には未反応のシクロペンタジエンおよび分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、固形分の1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基およびディールス・アルダー反応して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基およびディールス・アルダー反応して生成したオレフィン由来のプロトンピーク(4.9~6.8ppm)が30:70の積分比率で観察された。熱重量分析 (TA Instruments社SDT Q600を使用、窒素流量 100 ml/min, 20℃/minで昇温)の結果、340℃で28%の重量減少が観測され、樹脂X-1中におけるシクロペンタジエンの付加量(質量%)が確認された。 <Synthesis of Resin X-1>
Resin (A-1) 800 mg, 2,6-bis (1,1-dimethylethyl) -4-methylphenol 50 mg, and dicyclopentadiene 8 g were added to diphenyl ether 4 g.
The resulting solution was heated to 180 ° C. in a nitrogen stream and stirred for 3 hours. After completion of the stirring, the reaction solution was added to 200 ml of electronic grade methanol, and the precipitated solid was collected by filtration and dried, and the white solid target product (resin X -1) 820 mg was obtained. When the obtained resin was analyzed by GPC, it was Mw = 11.5 * 10 < 4 > , Mn = 5.29 * 10 < 4 > . Unreacted cyclopentadiene and components having a molecular weight of 3 million or more were not observed in the solid. When 1 H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group formed by polymerization of a vinyl group and a proton peak derived from an alkyl group formed by Diels-Alder reaction (0.2 to 3.0 ppm) and a proton peak (4.9 to 6.8 ppm) derived from an olefin produced by the remaining vinyl group and Diels-Alder reaction was observed at an integration ratio of 30:70. As a result of thermogravimetric analysis (TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rising at 20 ° C / min), a 28% weight loss was observed at 340 ° C, and cyclopentadiene in resin X-1 The addition amount (mass%) of was confirmed.
樹脂(A-2)800mg、2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール50mg、ペンタメチルシクロペンタジエン800mgをジフェニルエーテル4gに加えた。得られた溶液を窒素気流中180℃に加熱し、3時間攪拌した。反応液を電子グレードメタノール200mlに加え、析出固体を濾取、乾燥し、一般式(F-2)で表されるディールス・アルダー反応付加部を有する白色固体の目的物(樹脂X-2)910mgを得た。得られた樹脂をGPCで分析すると、Mw=9.47×104、Mn=5.86×104であった。固形物中には未反応のペンタメチルシクロペンタジエンおよび分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、固形分の1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基およびディールス・アルダー反応して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基およびディールス・アルダー反応して生成したオレフィン由来のプロトンピーク(4.9~6.8ppm)が85:15の積分比率で観察された。熱重量分析 (TA Instruments社SDT Q600を使用、窒素流量 100 ml/min, 20℃/minで昇温)の結果、336℃で44%の重量減少が観測され、樹脂X-2中におけるペンタメチルシクロペンタジエンの付加量(質量%)が確認された。 <Synthesis of Resin X-2>
Resin (A-2) 800 mg, 2,6-bis (1,1-dimethylethyl) -4-methylphenol 50 mg, and pentamethylcyclopentadiene 800 mg were added to diphenyl ether 4 g. The resulting solution was heated to 180 ° C. in a nitrogen stream and stirred for 3 hours. The reaction solution was added to 200 ml of electronic grade methanol, and the precipitated solid was collected by filtration, dried, and 910 mg of the desired product (resin X-2) having a Diels-Alder reaction addition portion represented by the general formula (F-2). Got. When the obtained resin was analyzed by GPC, M w = 9.47 × 10 4 and M n = 5.86 × 10 4 . In the solid, unreacted pentamethylcyclopentadiene and components having a molecular weight of 3 million or more were not observed. When 1 H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group formed by polymerization of vinyl group and a proton peak derived from an alkyl group formed by Diels-Alder reaction (0.2 to 3.0 ppm) and a proton peak (4.9 to 6.8 ppm) derived from an olefin produced by the remaining vinyl group and Diels-Alder reaction was observed at an integral ratio of 85:15. As a result of thermogravimetric analysis (TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rising at 20 ° C / min), 44% weight loss was observed at 336 ° C, and pentamethyl in resin X-2 The addition amount (mass%) of cyclopentadiene was confirmed.
樹脂(A-2)800mg、2,6-ビス(1,1-ジメチルエチル)-4-メチルフェノール50mg、ペンタメチルシクロペンタジエン240mgをジフェニルエーテル4gに加えた。得られた溶液を窒素気流中180℃に加熱し、3時間攪拌した。反応液を電子グレードメタノール200mlに加え、析出固体を濾取、乾燥し、一般式(F-2)で表されるディールス・アルダー反応付加部を有する白色固体の目的物(樹脂X-3)910mgを得た。得られた樹脂をGPCで分析すると、Mw=10.6×104、Mn=5.49×104であった。固形物中には未反応のペンタメチルシクロペンタジエンおよび分子量300万以上の成分は観測されなかった。重クロロホルムを測定溶媒として、固形分の1H-NMRスペクトルを測定したところ、ビニル基が重合して生成したアルキル基およびディールス・アルダー反応して生成したアルキル基由来のプロトンピーク(0.2~3.0ppm)と、残存したビニル基およびディールス・アルダー反応して生成したオレフィン由来のプロトンピーク(4.9~6.8ppm)が60:40の積分比率で観察された。熱重量分析 (TA Instruments社SDT Q600を使用、窒素流量 100 ml/min, 20℃/minで昇温)の結果、330℃で14%の重量減少が観測され、樹脂X-3中におけるペンタメチルシクロペンタジエンの付加量(質量%)が確認された。 <Synthesis of Resin X-3>
800 mg of Resin (A-2), 50 mg of 2,6-bis (1,1-dimethylethyl) -4-methylphenol and 240 mg of pentamethylcyclopentadiene were added to 4 g of diphenyl ether. The resulting solution was heated to 180 ° C. in a nitrogen stream and stirred for 3 hours. The reaction solution was added to 200 ml of electronic grade methanol, and the precipitated solid was collected by filtration, dried, and 910 mg of the desired product (resin X-3) as a white solid having a Diels-Alder reaction addition part represented by the general formula (F-2). Got. When the obtained resin was analyzed by GPC, it was Mw = 10.6 × 10 4 and M n = 5.49 × 10 4 . In the solid, unreacted pentamethylcyclopentadiene and components having a molecular weight of 3 million or more were not observed. When 1 H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group formed by polymerization of a vinyl group and a proton peak derived from an alkyl group formed by Diels-Alder reaction (0.2 to 3.0 ppm) and a proton peak (4.9 to 6.8 ppm) derived from an olefin produced by the reaction of the remaining vinyl group and Diels-Alder was observed at an integration ratio of 60:40. As a result of thermogravimetric analysis (TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rise at 20 ° C / min), 14% weight loss was observed at 330 ° C, and pentamethyl in resin X-3 The addition amount (mass%) of cyclopentadiene was confirmed.
なお、表1中におけるジエンBの付加量は、樹脂X中におけるジエンBの質量%(wt%)である。 With reference to the above production example, Resins X-4 to X-12 were synthesized. In addition, Table 1 shows the types of the resin A and the diene compound used for the synthesis of each resin, the weight average molecular weight, and the number average molecular weight.
In addition, the addition amount of the diene B in Table 1 is the mass% (wt%) of the diene B in the resin X.
なお、例示化合物(I-s)~(I-aa)は、上記例示化合物(I-k)などの製造方法および特開2008-210970号公報の合成方法を参照して合成した。 The polymerization conditions shown in Table 2 using the compounds (Is) to (I-aa) which are exemplary compounds of the compound (X) described above with reference to the production methods of the resins A-1 to A-5. Polymerization was carried out with (polymerization solvent, temperature). Table 2 shows the weight average molecular weight and number average molecular weight of the polymer obtained by the polymerization reaction.
Exemplified compounds (Is) to (I-aa) were synthesized with reference to the production method of the exemplified compound (Ik) and the like and the synthesis method of JP-A-2008-210970.
特開2007-161788号公報に記載の方法に従い、1,3-ジエチニルアダマンタンの重合体(G-1)を合成した。得られた重合体をGPCで分析すると、Mw=1.37×104、Mn=0.39×104であった。
重合体(G-1)12.9gをトルエン30mLに溶解させ、このトルエン溶液を0℃に冷却しながらDIBAL-H(1M,ヘキサン溶液)175mLを加えた。その後、室温で3時間攪拌した。次に、飽和塩化アンモニウム水溶液230mLを冷却し、ここに反応液を加えて、ろ過した後、ろ液を酢酸エチルで抽出した。有機層を硫酸ナトリウムで乾燥した後、溶液を減圧濃縮した。得られた粗生成物を少量のテトラヒドロフランに溶解させ、その溶液をメタノール300mLに加え、析出固体を濾取、乾燥し、白色固体の目的物(樹脂H-1)10.3gを得た。得られた樹脂をGPCで分析すると、Mw=1.35×104、Mn=0.39×104であった。 <Synthesis of Resin H-1>
According to the method described in JP-A No. 2007-161788, a 1,3-diethynyladamantane polymer (G-1) was synthesized. When the obtained polymer was analyzed by GPC, it was Mw = 1.37 * 10 < 4 > , Mn = 0.39 * 10 < 4 > .
12.9 g of the polymer (G-1) was dissolved in 30 mL of toluene, and 175 mL of DIBAL-H (1M, hexane solution) was added while the toluene solution was cooled to 0 ° C. Then, it stirred at room temperature for 3 hours. Next, 230 mL of a saturated aqueous ammonium chloride solution was cooled, the reaction solution was added thereto and filtered, and then the filtrate was extracted with ethyl acetate. After drying the organic layer with sodium sulfate, the solution was concentrated under reduced pressure. The obtained crude product was dissolved in a small amount of tetrahydrofuran, the solution was added to 300 mL of methanol, and the precipitated solid was collected by filtration and dried to obtain 10.3 g of the desired product (resin H-1) as a white solid. When the obtained resin was analyzed by GPC, M w = 1.35 × 10 4 and M n = 0.39 × 10 4 .
特開2007-161786号公報に記載の方法に従い、4,9-ジエチニルジアマンタンの重合体(G-2)を合成した。得られた重合体をGPCで分析すると、Mw=1.66×104、Mn=0.54×104であった。
上記の重合体(G-1)の代わりに重合体(G-2)を用いた以外は、樹脂(H-1)の合成と同様に反応を行い、樹脂(H-2)を得た。得られた樹脂をGPCで分析すると、Mw=1.65×104、Mn=0.51×104であった。 <Synthesis of Resin H-2>
According to the method described in JP-A-2007-161786, a polymer (G-2) of 4,9-diethynyldiamantane was synthesized. When the obtained polymer was analyzed by GPC, it was Mw = 1.66 * 10 < 4 > , Mn = 0.54 * 10 < 4 > .
A reaction was carried out in the same manner as the synthesis of the resin (H-1) except that the polymer (G-2) was used instead of the polymer (G-1) to obtain a resin (H-2). When the obtained resin was analyzed by GPC, it was Mw = 1.65 * 10 < 4 > , Mn = 0.51 * 10 < 4 > .
特表2003-520864号公報に記載の方法に準じて、ビニル基を有するポリアリーレンエーテル(樹脂H-3)を合成した。 <Synthesis of Resin H-3>
A polyarylene ether having a vinyl group (resin H-3) was synthesized according to the method described in JP-T-2003-520864.
特表2004-504455号公報に記載のテトラキス(トラニル)アダマンタンの合成法において、フェニルアセチレンの代わりにフェニルアセチレンと(トリメチルシリル)アセチレンの混合物(等モル量)を用いて化合物(G-4)を合成した。次に、特開2007-314778号公報に記載の方法に従い、(トリメチルシリル)エチニル基をビニル基に変換し、化合物(H-4)を得た。
なお、以下の式中のR1はフェニル基とトリメチルシリル基の混合物であり、R2はフェニルエチニル基とビニル基の混合物である。 <Synthesis of Compound H-4>
In the method for synthesizing tetrakis (tranyl) adamantane described in JP-T-2004-504455, compound (G-4) is synthesized using a mixture (equal molar amount) of phenylacetylene and (trimethylsilyl) acetylene instead of phenylacetylene. did. Next, the (trimethylsilyl) ethynyl group was converted to a vinyl group according to the method described in JP-A-2007-314778 to obtain compound (H-4).
In the following formula, R 1 is a mixture of a phenyl group and a trimethylsilyl group, and R 2 is a mixture of a phenylethynyl group and a vinyl group.
国際公開第2005-019305号パンフレットに記載の方法に準じて、ビニル基を有するポリベンゾオキサゾール(樹脂H-5)を合成した。 <Synthesis of Resin H-5>
Polybenzoxazole (resin H-5) having a vinyl group was synthesized according to the method described in International Publication No. 2005-019305 pamphlet.
なお、表3中におけるジエンBの付加量は、樹脂X中におけるジエンBの質量%(wt%)である。 With reference to the production examples of Resin X-1 to Resin X-3, Resins X-23 to X-28 were synthesized using Resins H-1 to H-5. Table 3 shows the types of resin H and diene compound used in the synthesis of each resin, and the weight average molecular weight and number average molecular weight.
The amount of diene B added in Table 3 is the mass% (wt%) of diene B in the resin X.
上記で得られた樹脂を下記表4に示すように溶剤に溶解させ、それぞれについて固形分濃度8質量%の溶液を調製した。得られた溶液を0.1μmのテトラフルオロエチレン製フィルターでろ過した後、スピンコート法で4インチシリコンウエハ上に塗布し、ホットプレート上にて110℃で1分間、ついで200℃で1分間、基板を予備乾燥し、膜厚400nmの塗布膜を形成させた。 <Preparation of composition>
The resin obtained above was dissolved in a solvent as shown in Table 4 below, and a solution having a solid content of 8% by mass was prepared for each. The obtained solution was filtered through a 0.1 μm tetrafluoroethylene filter, and then applied onto a 4 inch silicon wafer by spin coating, and then on a hot plate at 110 ° C. for 1 minute, then at 200 ° C. for 1 minute. The substrate was preliminarily dried to form a coating film having a thickness of 400 nm.
(1)加熱
光洋サーモ社製クリーンオーブンCLH-21CD(III)により、窒素雰囲気下、クリーンオーブン中で400℃、60分間加熱した。
(2)EB照射
ウシオ電機社製Mini-EBにてAr雰囲気、圧力100kPa、基板温度350℃の条件で、電子加速電圧20keV、電子線ドーズ量1μCcm-2を5分間照射した。
(3)UV照射
ウシオ電機社製誘電体バリア放電方式エキシマランプUER20-172を用い、窒素気流下、350℃のホットプレート上で172nmの波長光100mJ/cm2を5分照射した。 The obtained coating film was cured by any of the following methods.
(1) Heating It was heated in a clean oven at 400 ° C. for 60 minutes under a nitrogen atmosphere by a clean oven CLH-21CD (III) manufactured by Koyo Thermo.
(2) EB irradiation An electron acceleration voltage of 20 keV and an electron beam dose of 1 μCcm −2 were irradiated for 5 minutes under the conditions of Ar atmosphere, pressure of 100 kPa, and substrate temperature of 350 ° C. using Mini-EB manufactured by USHIO.
(3) UV irradiation Using a dielectric barrier discharge excimer lamp UER20-172 manufactured by Ushio Electric Co., Ltd., irradiation was carried out for 5 minutes on a hot plate at 350 ° C. under a nitrogen stream at a wavelength of 100 mJ / cm 2 at 172 nm.
なお、表4中において、界面活性剤の含有量は、組成物(塗布液)全量に対する質量%を表す。一方、密着促進剤の含有量は、組成物(塗布液)中の全固形物に対する質量%で表される。 The obtained cured film was evaluated by the following method. The results are shown in Table 4.
In Table 4, the content of the surfactant represents mass% with respect to the total amount of the composition (coating liquid). On the other hand, the content of the adhesion promoter is represented by mass% with respect to the total solids in the composition (coating liquid).
フォーディメンジョンズ製水銀プローバおよび横川ヒューレットパッカード製のHP4285ALCRメーターを用いて、1MHzにおける容量値(測定温度25℃)から算出した。
<ヤング率>
MTS社ナノインデンターSA2を使用してヤング率を測定した。
<比誘電率の経時安定性>
得られたウエハを23℃、40%RH(相対湿度)の雰囲気に放置し,4週間後に比誘電率を上記の方法で測定した。比誘電率変化量が±0.1の範囲にあるものを○、範囲にないものを×と表記した。
<膜形成後の耐熱性の評価>
耐熱性の評価は、得られた膜を空気中400℃、60秒加熱し、膜厚変化率を測定することによって行った。値が0に近い値である塗膜ほど、耐熱性が良いといえる。実施例1および2はそれぞれ6.8%、4.8%であり、比較例1および2はそれぞれ10.1、8.9%であった。 <Relative permittivity>
Using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, the capacity value at 1 MHz (measurement temperature: 25 ° C.) was used for calculation.
<Young's modulus>
The Young's modulus was measured using MTS nanoindenter SA2.
<Stability of relative permittivity over time>
The obtained wafer was left in an atmosphere of 23 ° C. and 40% RH (relative humidity), and the relative dielectric constant was measured by the above method after 4 weeks. Those in which the relative dielectric constant change amount was in the range of ± 0.1 were indicated as ◯, and those not in the range were indicated as ×.
<Evaluation of heat resistance after film formation>
Evaluation of heat resistance was performed by heating the obtained film at 400 ° C. for 60 seconds in air and measuring the rate of change in film thickness. It can be said that the heat resistance is better as the coating film has a value close to 0. Examples 1 and 2 were 6.8% and 4.8%, respectively, and Comparative Examples 1 and 2 were 10.1 and 8.9%, respectively.
一方、硬化処理時にジエン化合物を放出しない比較例1および2において得られた膜は、比誘電率は高く、かつ、ヤング率も低かった。比誘電率の経時安定性および耐熱性の点でも劣っていた。 From the results of Table 4, when the film forming composition of the present invention is used, the relative permittivity is low by various curing methods such as heating, EB irradiation, UV irradiation, and the relative permittivity is stable over time and heat resistance. It was confirmed that an excellent film having a high Young's modulus can be obtained.
On the other hand, the films obtained in Comparative Examples 1 and 2 that did not release the diene compound during the curing treatment had a high relative dielectric constant and a low Young's modulus. It was also inferior in terms of the relative dielectric constant stability over time and heat resistance.
50ml三口フラスコにbicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane(下式)2.79g、テトラエトシキシラン625mg、メチルトリエトキシシラン2.32g、シュウ酸100mg、イソプロピルアルコール12ml、ブタノール8ml、イオン交換水3mlを入れ、7時環加熱還流した。放冷後0.1μmのテトラフルオロエチレン製フィルターでろ過した。
得られた組成物をスピンコート法で4インチシリコンウエハ上に塗布後、ホットプレート上にて80℃で5分間、200℃で5分間基板を乾燥し、さらに窒素雰囲気のオーブン中にて400℃で60分間焼成して、膜厚400nmの膜を形成させた。
得られた膜について上記と同様の測定を行ったところ、比誘電率は2.1、ヤング率は5.4MPa、誘電率の経時安定性は○であった。 <Example 29>
Bicyclo [2.2.1] hept-5-en-2-yltrimethoxysilane (following formula) 2.79 g, tetraethoxysilane 625 mg, methyltriethoxysilane 2.32 g, oxalic acid 100 mg, isopropyl alcohol 12 ml, butanol 8 ml in a 50 ml three-necked flask Then, 3 ml of ion-exchanged water was added, and the mixture was heated to reflux for 7 hours. After cooling, the mixture was filtered through a 0.1 μm tetrafluoroethylene filter.
The obtained composition was applied on a 4-inch silicon wafer by spin coating, and then the substrate was dried on a hot plate at 80 ° C. for 5 minutes and at 200 ° C. for 5 minutes, and further in an oven in a nitrogen atmosphere at 400 ° C. Was baked for 60 minutes to form a film having a thickness of 400 nm.
When the same measurement as described above was performed on the obtained film, the relative dielectric constant was 2.1, the Young's modulus was 5.4 MPa, and the temporal stability of the dielectric constant was ○.
得られた硬化膜をウエハごと2.0cm×0.5cmの矩形にカットしてガス吸着測定用セルに入れ、QUANTACHROME社製細孔分布・比表面積測定装置AUTOSORB‐1を用いて窒素ガスによるガス吸着測定を行った。測定後のデータはN2/DFT(N2 at 77K on silica(cylinder pore, NLDFT equibrium model))法により解析し、得られた細孔分布(空孔分布)の最大頻度径(最大ピーク)を最大分布直径とした。
実施例1、2、17の最大頻度径はそれぞれ2.5nm、2.8nm、1.9nmであり、比較例1および2はそれぞれ7.8nm、9.2nmであった。 <Measurement of hole diameter>
The obtained cured film is cut into a 2.0 cm × 0.5 cm rectangle together with the wafer and placed in a gas adsorption measurement cell, and a gas with nitrogen gas is used with a pore distribution / specific surface area measurement device AUTOSORB-1 manufactured by QUANTACHROME. Adsorption measurement was performed. The data after measurement is analyzed by the N2 / DFT (N2 at 77K on silica (Cylinder pore, NLDFT equilibrium model)) method, and the maximum frequency diameter (maximum peak) of the obtained pore distribution (hole distribution) is the maximum distribution. The diameter.
The maximum frequency diameters of Examples 1, 2, and 17 were 2.5 nm, 2.8 nm, and 1.9 nm, respectively, and Comparative Examples 1 and 2 were 7.8 nm and 9.2 nm, respectively.
Claims (16)
- 加熱、光照射、放射線照射またはそれらの組み合わせにより、その一部が脱離して揮発性成分を生じ、残部に不飽和基を生成する官能基を有する化合物(X)を含有する組成物。 A composition containing a compound (X) having a functional group that partially generates a volatile component by heating, light irradiation, radiation irradiation, or a combination thereof to generate a volatile component, and the remainder generates an unsaturated group.
- 前記化合物(X)が、共役ジエン構造とジエノフィル構造とのディールス・アルダー反応によって形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応が進行して前記共役ジエン構造と前記ジエノフィル構造が生成されるディールス・アルダー反応付加部を有し、かつ、シロキサン構造を有する化合物である請求項1に記載の組成物。 The compound (X) is formed by a Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and a reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof, and the conjugated diene structure and the above-mentioned The composition according to claim 1, which is a compound having a Diels-Alder reaction addition part capable of generating a dienophile structure and having a siloxane structure.
- 前記化合物(X)が、ジエノフィル構造を有し、かつ、シロキサン構造を有する化合物(A)と、共役ジエン構造を有する化合物(B)とのディールス・アルダー反応により形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応を介して前記共役ジエン構造を有する化合物(B)を放出する化合物である、請求項2に記載の組成物。 The compound (X) is formed by a Diels-Alder reaction between a compound (A) having a dienophile structure and a siloxane structure and a compound (B) having a conjugated diene structure, and heating, light irradiation, radiation The composition of Claim 2 which is a compound which discharge | releases the compound (B) which has the said conjugated diene structure through reverse Diels-Alder reaction by irradiation or those combinations.
- 前記シロキサン構造を有する化合物(A)が、m個のRSi(O0.5)3ユニット(mは8~16の整数を表し、Rは、それぞれ独立に、水素原子または置換基を表す。)を有し、各ユニットが各ユニットにおける酸素原子を共有して他のユニットに連結しカゴ構造を形成している化合物(I)またはその重合体である、請求項3に記載の組成物。 The compound (A) having the siloxane structure has m RSi (O 0.5 ) 3 units (m represents an integer of 8 to 16, and each R independently represents a hydrogen atom or a substituent). The composition according to claim 3, wherein each unit is Compound (I) or a polymer thereof, wherein each unit shares an oxygen atom in each unit and is linked to another unit to form a cage structure.
- 前記化合物(I)が、下記一般式(Q-1)~(Q-7)のいずれかで表される化合物である、請求項4に記載の組成物。
- 前記共役ジエン構造を有する化合物(B)が、一般式(B-1)~一般式(B-3)のいずれかで表される化合物である、請求項3~5のいずれかに記載の組成物。
一般式(B-1)および一般式(B-2)中、Wは、-O-、-C(O)-、-C(O)O-、-S(O)-、-S(O)2-、-C(X17)(X18)-、または、-N(X19)-を表す。X17~X19は、それぞれ独立に、水素原子または置換基を表す。) 6. The composition according to claim 3, wherein the compound (B) having a conjugated diene structure is a compound represented by any one of the general formulas (B-1) to (B-3). object.
In the general formulas (B-1) and (B-2), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (X 17 ) (X 18 ) —, or —N (X 19 ) —. X 17 to X 19 each independently represents a hydrogen atom or a substituent. ) - 前記化合物(X)中における前記共役ジエン構造を有する化合物(B)の付加量が、前記化合物(X)全量に対して、5~80質量%である請求項3~6のいずれかに記載の組成物。 The addition amount of the compound (B) having the conjugated diene structure in the compound (X) is 5 to 80% by mass with respect to the total amount of the compound (X). Composition.
- さらに、溶剤を含む請求項1~7のいずれかに記載の組成物。 The composition according to any one of claims 1 to 7, further comprising a solvent.
- 絶縁膜形成用途に用いられる請求項1~8のいずれかに記載の組成物。 The composition according to any one of claims 1 to 8, which is used for insulating film formation.
- 請求項1~9いずれかに記載の組成物を基板上に塗布した後、硬膜することを特徴とする絶縁膜の製造方法。 A method for producing an insulating film, comprising applying the composition according to any one of claims 1 to 9 on a substrate and then hardening the composition.
- 請求項10に記載の製造方法を用いて製造された絶縁膜。 An insulating film manufactured using the manufacturing method according to claim 10.
- 請求項11に記載の絶縁膜を用いて製造された電子デバイス。 An electronic device manufactured using the insulating film according to claim 11.
- 加熱、光照射、放射線照射またはそれらの組み合わせにより、その一部が脱離して揮発性成分を生じ、残部に不飽和基を生成する官能基を有する化合物。 A compound having a functional group that is partially desorbed by heating, light irradiation, radiation irradiation, or a combination thereof to generate a volatile component, and the remaining part generates an unsaturated group.
- 共役ジエン構造とジエノフィル構造とのディールス・アルダー反応によって形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応が進行して前記共役ジエン構造と前記ジエノフィル構造が生成されるディールス・アルダー反応付加部を有し、かつ、シロキサン構造を有する樹脂。 Diels formed by a Diels-Alder reaction between a conjugated diene structure and a dienophile structure, and a reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof to produce the conjugated diene structure and the dienophile structure. -Resin which has an alder reaction addition part and has a siloxane structure.
- ジエノフィル構造を有し、かつ、シロキサン構造を有する化合物(A)と、共役ジエン構造を有する化合物(B)とのディールス・アルダー反応により形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応を介して前記共役ジエン構造を有する化合物(B)を放出する樹脂。 Formed by the Diels-Alder reaction between the compound (A) having a dienophile structure and a siloxane structure and the compound (B) having a conjugated diene structure, and reversed by heating, light irradiation, radiation irradiation or a combination thereof. Resin that releases the compound (B) having the conjugated diene structure through Diels-Alder reaction.
- 一般式(Q-1)~(Q-7)のいずれかで表される化合物またはその重合体と、一般式(B-1)~(B-3)のいずれかで表される化合物とのディールス・アルダー反応により形成され、加熱、光照射、放射線照射またはそれらの組み合わせにより逆ディールス・アルダー反応を介して前記一般式(B-1)~(B-3)のいずれかで表される化合物を放出する樹脂。
一般式(B-1)および一般式(B-2)中、Wは、-O-、-C(O)-、-C(O)O-、-S(O)-、-S(O)2-、-C(X17)(X18)-、または、-N(X19)-を表す。X17~X19は、それぞれ独立に、水素原子または置換基を表す。) A compound represented by any one of the general formulas (Q-1) to (Q-7) or a polymer thereof and a compound represented by any one of the general formulas (B-1) to (B-3): A compound formed by a Diels-Alder reaction and represented by any one of the general formulas (B-1) to (B-3) via a reverse Diels-Alder reaction by heating, light irradiation, radiation irradiation or a combination thereof Releasing resin.
In the general formulas (B-1) and (B-2), W represents —O—, —C (O) —, —C (O) O—, —S (O) —, —S (O ) 2 —, —C (X 17 ) (X 18 ) —, or —N (X 19 ) —. X 17 to X 19 each independently represents a hydrogen atom or a substituent. )
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US (1) | US8530583B2 (en) |
EP (1) | EP2357204A4 (en) |
JP (1) | JP5401118B2 (en) |
KR (1) | KR20110106298A (en) |
TW (1) | TWI498344B (en) |
WO (1) | WO2010067683A1 (en) |
Cited By (2)
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JP2010189571A (en) * | 2009-02-19 | 2010-09-02 | Fujifilm Corp | Compound having addion portion formed by diels-alder reaction |
WO2019208471A1 (en) * | 2018-04-27 | 2019-10-31 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-added film, resin-added metal foil, metal-clad layered plate, and wiring plate |
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WO2010005937A1 (en) * | 2008-07-08 | 2010-01-14 | Fujifilm Electronic Materials U.S.A., Inc. | Additives to prevent degradation of cyclic alkene derivatives |
JP5821761B2 (en) * | 2011-04-20 | 2015-11-24 | セントラル硝子株式会社 | Siloxane compounds and cured products thereof |
CN103172657B (en) * | 2011-12-26 | 2016-03-30 | 北京化工大学 | Containing the functionalized cage modle polyhedral polysilsesquioxane and preparation method thereof of alkynyl |
WO2013176845A1 (en) * | 2012-05-21 | 2013-11-28 | Agilent Technologies, Inc. | Retro diels alder reaction as a cleavable linker in dna/rna applications |
JP2016172244A (en) * | 2015-03-18 | 2016-09-29 | リンテック株式会社 | Coating liquid supply device, coating liquid supply method, manufacturing method of lamination body, manufacturing method of gas barrier film, lamination body, and gas barrier film |
CN109233294B (en) * | 2018-08-28 | 2020-04-24 | 淮阴工学院 | Organic silicon micro-porous ultralow dielectric film and preparation method thereof |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010189571A (en) * | 2009-02-19 | 2010-09-02 | Fujifilm Corp | Compound having addion portion formed by diels-alder reaction |
WO2019208471A1 (en) * | 2018-04-27 | 2019-10-31 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, resin-added film, resin-added metal foil, metal-clad layered plate, and wiring plate |
JPWO2019208471A1 (en) * | 2018-04-27 | 2021-07-01 | パナソニックIpマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
Also Published As
Publication number | Publication date |
---|---|
JP2010159385A (en) | 2010-07-22 |
EP2357204A4 (en) | 2012-06-27 |
US20110245416A1 (en) | 2011-10-06 |
JP5401118B2 (en) | 2014-01-29 |
TWI498344B (en) | 2015-09-01 |
KR20110106298A (en) | 2011-09-28 |
TW201030031A (en) | 2010-08-16 |
EP2357204A1 (en) | 2011-08-17 |
US8530583B2 (en) | 2013-09-10 |
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